Electroplating Theory & Concepts - Beginners Edition

Chromium Plating
By Nabil Zaki
Vice President of Technology
MacDermid, Inc.
Kearny, New Jersey
Despite the simplicity of their formulations, chromium plating baths are more complicated to operate than
most plating baths, and they require rigorous controls.
CHROMIC-ACID-BASED BATHS (Hexavalent type)
In plating from hexavalent chromium baths, sulfate and fluoride ions act as catalysts. Temperature, current
density and bath composition affect the film characteristics and current efficiency. These parameters are
therefore carefully controlled in order to obtain specific deposit properties and plating rates.
Thicknesses of deposits vary from 0.25 to 0.5 micron (0.001 inch), or more for hard chromium plating.
Bath Composition
Chromic acid and sulfate are the necessary ingredients. Chromic-to-sulfate ratios range from 75:1 to 250:1.
The composition depends primarily on whether the bath is co-catalyzed, e.g. with fluorides, fluosili-cates or
fluoborates, and on the application (decorative or hard chromium).
Plumbing fixtures and fitting shave been attractively finished using a tribalent chromium plating solution.
(Photo courtesy MacDermid Inc., Kearny, NJ)
Cr+6 is the source of chromium depos-ited from these baths. Chromic acid, Cr0 3, is the main component in
solution make-up. Cr+6 is reduced to Cr+3, which in turn is reduced to unstable Cr+2 and further to Cr0.
Some Cr+3 is normally found in operating baths, and indeed in the absence of Cr +3, little or no deposit is
obtained. The introduction of small amounts of reducing agents to a new solution helps in bath start-up.
An amount of Cr+3 exceeding two-three pct of the chromic acid content, however, reduces cathode
efficiency and causes a variety of plating problems.
The presence of other oxides of metals, e.g. iron, copper and nickel, combined with Cr +3, hurts bath
performance.
While the simple chromic-sulfate baths produce about 12 pct efficiency, co-catalyzed baths may deposit at
efficiencies up to 22 pct. For a given composition, there is an optimum range of current density and
temperature that produces a bright deposit. When a specific composition is found to produce the most
desirable results for a given application, it should then be tightly maintained by periodic analytical and
control methods.
Table I—Single Catalyst Plating Bath Parameters:
Decorative Hard (heavy) plating

Chromic Acid 225-300 g/liter 250-400
Chromic/Sulfate ratio 100:1 to 150:1 75:1 to 100:1
Temperature 35-46C 49-65C (120-150F)
Current density 7.0-15 A/dm2 22-100 A/dm2
Cathode efficiency 6-12 pct 10-15 pct
Co-Catalyzed and High-Speed Baths

Chromic Acid 210-270 g/liter 200-300 g/liter
Temperature 35-55C 43-55C
Currently Density 7.0-15 A/dm2 22-90 A/dm2
Typical single-catalyst and co-catalyst plating baths have the parameters shown in Table I.
In single-catalyst baths, cathode efficiency increases proportionally with chromic acid concentration, up to
250 g/ liter, and thereafter decreases (Fig. 1). Solutions with higher concentrations of chromic acid tolerate
a higher level of trivalent chromium and iron oxide contaminants. Additions of secondary catalyst improve
cathode efficiency at high concentrations of chromic acid, up to 300 g/liter.
Analyses of chromic acid (Cr +6), sulfate, secondary co-catalyst, e.g. fluoride, as well as trivalent chromium
(Cr+3) are needed to maintain the bath composition within the required limits.
Temperature
Temperature is closely related to current density in its effect on brightness and coverage of deposit.
Generally, the higher the current density, the higher the temperature requirement (Fig. 2). An optimum
temperature range exists for a given concentration of chromic acid. Below or above that range, dull deposits
result.
In general, for decorative baths, the range is 35C (95F) to 46C (115F). For hard chromium, the range is 49C
(120F) to 65.5C (150F).
Since the chromic acid solutions used are fairly concentrated and viscous, stratification may occur. This
results in uneven temperature distribution within the solution. Agitation is therefore required to equalize
the bath temperature, to produce uniform brightness, and in the case of hard chromium, to improve deposit
hardness.
Preheating of parts to optimum bath temperature may be needed before they are introduced to the plating
tank, and in rare instances cooling of parts may be required, in order to insure uniformity of deposit. Using
both heating and cooling coils in the same tank may be necessary to maintain a precise temperature.
1. Effect of chromic acid concentration on current efficiency.
Current Density
At given solution composition and temperature, current density affects cathode efficiency, brightness and
hardness. Generally, the optimum current density is recommended by the manufacturer of the plating
chemicals used. At too-high current densities, burning or roughness of deposit occur. At low current
densities, lack of chromium coverage can be expected.
Be sure to use the proper current source. Deposit hazing and/or peeling can be traced to electrical
problems, especially in conventional chromic-sulfate (single catalyst) baths.
Three-phase rectifiers with a maximum of five pct AC ripple should supply an uninterrupted flow of current
throughout the plating cycle. Standard current densities are in the range of 7.75-15.5 A/dm 2 (0.5 to 1.0 asi)
for decorative plating, and 23.25 to 100 A/dm2 (1.5 to 6.5 asi) for hard chromium plating.
Anodes
Insoluble lead or lead-antimony alloy are used. Plating of inside diameters and recessed areas may require
that conforming anodes be fixtured at close proximity (0.5-1 inch) to the surface to be plated.
2. At constant temperature, cathode efficiency increases with current density. at constant current density,
cathode efficiency decreases with temperature.
In hard chromium plating, the closer the anode-to-cathode distance, the better the deposit distribution.
Lead anodes ideally should be 90 pct as long as the cathodes. Tops and bottoms should be slightly below and
above the tops and bottoms of the cathodes (parts) respectively to prevent excessive build-up at the plated
ends.
Properly operating lead anodes form a layer of dark brown lead oxide. A yellow or light colored coating on
the anodes indicates a build-up of lead chromate, which results from too little or no current flow, such as
during idle periods. This light colored layer has poor electrical conductivity.
Cleaning and reactivating lead anodes can be performed chemically, using cleaners specially formulated for
that purpose. Once cleaned, the anodes should be properly rinsed and promptly returned to the tank. A
satisfactory distribution of anodes consists of three anodes two inches in diameter or four 1.5-inch-diameter
anodes per foot of anode bar.
Self-Regulating High-Speed Baths
This type of solution incorporates fluoride complexes such as silicofluorides, in addition to sulfates. Salts of
low solubility are selected and used to release the desired anions on a controlled basis. Mixtures containing
potassium or sodium silicofluoride, and dichromate, for example, regulate the release of fluorides by
common-ion effect. Mixtures of strontium sulfate and chromate regulate the release of sulfate.
Consequently, at higher temperatures, the cathode current efficiency increases as a result of the increased
solubility of catalysts in this type of bath.
Crack-Free Chromium
This is deposited from baths with low catalyst ratio and high concentration of chromic acid. Since the
deposit is hard and brittle, it cracks when subjected to strain, forming a macro-cracked layer.
Micro-Cracked Chromium
Microcracking is produced by proprietary dual-catalyst baths. The micro discontinuity of the chromium layer
results in spreading the corrosion potential that exists between chromium and an underlying nickel plate.
This reduces the anodic current flowing to any one location on the nickel, greatly retarding the rate of
corrosion. Crack densities of 27-50 cracks per millimeter are specified for optimum corrosion resistance.
Microporous Chromium
3. Membrane separating anode box from cathode compartment in trivalent

chromium plating
Microporous chromium also improves the corrosion resistance of nickel-chromium deposits, in a manner
similar to that just described for microcracked chromium. Regular hexavalent chromium deposits are
typically made microporous by one of two different methods.
The bright nickel layer can be topped with another thin layer of nickel plated from a bath containing a very
fine suspension of inert particles, which codeposit with the nickel. Chromium plated over this layer deposits
around these particles, creating a microporous structure.
Another way to produce microporous chromium is to lightly spray the surface of the chromium deposit with
a hard, fine abrasive material such as 60- or 80-mesh alumina, or sand. The brittle chromium deposit breaks
at the point of impact, forming micropores and exposing the bright nickel layer beneath the chromium.
For best corrosion resistance, the pore density in both cases must exceed 10,000 pores per square
centimeter.
Cleaning and Surface Preparation
Inadequate cleaning of the basis metal will lead to poor plating results. In decorative plating, hazy, pitted
or non-adherent nickel deposits will be obtained as a result of inadequate surface preparation. The thin
chromium deposit will magnify and reflect these defects.
Table II—Comparison of Working Parameters of Trivalent Sulfate Type Versus Hexavalent Baths
Trivalent Hexavalent
Concentration of chromium g/liter 5-6 100-250
pH 3.5-3.9 0
Temperature (C) 40-50 40-50
Current density A/dm2 4-9 10-15
Anode:Shielded Anode Lead (alloy) Lead (alloy)
Anode:Insoluable Anode Composite metal oxides
Throwing power Good Poor
Reaction to current interruption Tolerant Causes "white wash"
Effluent Low level of Cr3 High level of Cr3
Skin contact Mild effect, similar to nickel Strong acid burn and ulceration
Deposit structure Microporous Induces microdiscontinuities
Plating rate 0.1 micron/min at 7 A/dm2 0.1 micron/min at 10 A/dm2
Allowing a nickel plated surface to dry during transfer will passivate the nickel and produce milky, hazy or
no deposit when chromium plated. In hard chromium plating, surfaces of the basis metal should be free of
oil, grease or rust.
Etching of steel and stainless steel insures proper adhesion. The extent of etch needed depends on the
composition of the steel. Carbon steel should be etched for 15-30 sec and up to 45 sec if the steel has been
heat treated. Etching is best performed in non-catalyzed solutions of 210-225 g/liter (28-30 oz/gal) chromic
acid to prevent overetching by sulfate, and particularly by fluoride catalysts.
Reverse etching in the same plating bath usually introduces an excessive amount of iron into the bath and
should be avoided.
Trivalent chromium can be plated from cell with shielded anode (left) or from
single cell
TRIVALENT CHROMIUM PLATING
Toxicity of Cr+6, low current efficiency, poor metal distribution, burns in high-current-density areas, "white-
wash" and lack of coverage around holes are some of the problems associated with Cr +6 plating baths. These
factors led to the eventual development of a safer and more efficient system, based on trivalent chromium.
Trivalent chromium plating baths for decorative applications enjoyed a steady, although initially slow,
acceptance as a substitute for hexavalent chromium plating. Their main attraction lies in the fact that they
eliminate many of the shortcomings of hexavalent chromium solutions.
Bath Chemistry
Several advances in technology have taken place, making the process more readily acceptable to platers.
Single-Cell Trivalent Chromium
A major distinction between trivalent chromium processes is the chemistry used to prevent the formation
of hexavalent chromium at the anode during plating. This must be done, since hexavalent chromium is a
poison to all trivalent chromium plating processes.
Fig. 4 shows the anode configurations of the shielded anode type and single-cell trivalent chromium
plating. The single-cell process has built into its chemistry mechanisms to prevent the presence of
hexavalent chromium. No hexavalent can form at the anode, and if hexavalent chromium were added, the
chemistry of the single-cell bath would immediately convert the hex to tri. This ability to convert hex to
tri instantly permits continued deposition of chromium from the single-cell bath. The working parameters
of the two available versions of the single-cell process are shown in Table A. The room-tempera-ture
process produces deposits similar in color to that of stainless steel or pewter. The elevated-temperature
produces blue-white chromium almost identical in color to that from hexavalent baths. These solutions are
more sensitive to metallic impurities than hexavalent baths. The trivalent baths are easily purified.
Metallic impurities can be removed from single-cell baths by three methods. They can be plated out on
dummies. They can be removed quickly by adding a chemical purifier that precipitates large quantities of
metallic impurities at one time. Or they can be removed by ion exchange of a continuous basis. The
elevated-temperature single-cell process can produce deposits over 0.25 mil thick and maintain the
physical properties of hexavalent chromium deposits of similar thickness.
—Dr. Donald L. Snyder
World Wide Technical
Marketing Manager
Atotech USA
Cleveland, Ohio
There are currently at least three basic types of trivalent chromium baths available. A single electrolyte
bath, chloride or sulfate based, using graphite or composite anodes, and special additives to prevent
oxidation of trivalent chrome at the anodes (see accompanying "Single-Cell Trivalent Chrome" sidebar).
Another type, a sulfate-based system, uses shielded anodes. Conventional lead anodes are surrounded by
boxes sealed on one side by a selective ion membrane (Fig. 3, 4) and filled with dilute sulfuric acid.
The membrane used is a perfluorinated sulfonic acid, reinforced with an inert Teflon® fabric. The
membrane prevents the migrating trivalent chromium ions in the solution from reaching the anode, thus
preventing their oxidation to the hexavalent state.
The mechanism provides for excellent pH stability during plating. The bath is capable of producing light-
colored deposits very close to the appearance of deposits from hexavalent baths.
Table II summarizes the differences between Cr+6 and Cr+3 plating-bath parameters.
The sulfate type trivalent chromium solution is maintained as one would maintain a conventional bright
nickel bath. It utilizes a primary additive containing the trivalent chromium ion and a secondary additive
that contains grain refiners and brighteners. These materials are added on an ampere-hour basis, using
chemcial-feed pumps actuated by an ampere-hour meter.
Metallic impurities affect results as shown in Table III. These impurities can be plated out on dummies as
can be done with nickel baths, or through an external purification cell on a continuous basis. Ion exchange
columns can also be used, as well as precipitating agents followed by filtration.
A new insoluble catalytic anode has been developed for use in direct contact with the electrolyte of the
above sulfate-based system. The new anode is designed to maintain an electrode potential level that will
prevent oxidation of trivalent chrome at its surface. No selective oxidation additives are used in the
electrolyte. Consequently, the same high tolerance to metallic impurities, light colored deposits and pH
stability of this sulfate-based process are maintained. The users have a choice in selecting the shielded
anode or the insoluble direct contact type anodes with the same bath. This new development will make it
possible to use conforming and auxiliary anodes for plating of complex shaped configurations.
Deposit Characteristics
Trivalent chromium baths produce deposits that are inherently microdiscontinuous. Under about 0.65 micron
(25 millionths of an inch), trivalent chromium deposits are microporous. Typical density of the pores in a
microdiscontinuous deposit is 20,000 to 60,000 pores/sq cm. At higher thicknesses deposits are
microcracked.
The effect of microdiscontinuous chromium plating is to dissipate electrochemical corrosion current over a
wide surface area, thus improving corrosion resistance.
Room-temperature and sulfate-type, trivalent chromium processes plate at rates similar to those of
hexavalent chromium baths—about 0.1 micron or four millionths of an inch per minute.
The elevated-temperature chloride process plates at about 0.25 microns or 10 millionths of an inch per
minute.
The hardness of the deposit is similar to that of traditional hexavalent chromium—about 700 to 1,000
Vickers.
Another advantage of the trivalent chromium bath is its ability to tolerate current interruptions without
passivating or production of white "clouds" and hazes in the deposit. Stripping and replating over nickel can
be carried out easily, with no adverse effects.
Comparison of Effluent Treatment for Cr+6 and Cr+3
As trivalent chromium plating baths contain no hexavalent chromium, effluent treatment of the subsequent
rinse waters is both simpler and cheaper. Most hexavalent chromium baths contain about 250 g/liter of
chromic acid, equivalent to 130 g/liter of chromium metal. Even if a dragout rinse is used, the running-
water rinses usually contain a high concentration of Cr +6.
Table III—Metallic Impurities and Their Effects on Trivalent Baths

Metallic Impurity Maximum Tolerance, mg/liter Effect Produced If Exceeded
Ni 500 Darkening of deposit
Cr (VI) 30 Defects at low cd
Cu 30 White blooms at high cd
Zn 70 Darkness at low cd
Effluent treatment consists of acidification of the rinse waters to obtain the required pH of 2.5, followed by
reduction of the Cr+6 to Cr+3, using sulfur dioxide or sodium bisulfite, according to the following equation:
CrO3 + 2 NaHSO3 + 2H2SO4
Cr2(SO4)3 + Na2SO4 + 3H2O
Finally the solution is neutralized and this causes precipitation of chromium hydroxide.
The theoretical requirement is three kilograms of sodium bisulfite (60-62 pct SO 2) plus two-three kilograms
of sulfuric acid to reduce one kg of hexavalent chromium. A trivalent chromium electrolyte may contain
only five g/liter of chromium and require only neutralization to achieve precipitation. On precipitation, the
volume of sludge generated by a hexavalent chromium electrolyte is approximately 30 times greater than
that from a trivalent bath.
A dilution of about 100 times with rinse waters might produce an effluent from the plating process of about
50 ppm (mg/liter), of Cr+3 before any further dilution occurs from other sources in the factory.
Hexavalent Chromium Plating Troubleshooting Guide
Common Plating Problems. Identifying the origin of a plating deficiency is the necessary first step in solving
the problem. The basic causes of poor plating usually fall into three categories:
• Faulty bath chemistry.
• Improper temperature and/or current density.
• Poorly finished and/or inadequately cleaned basis-metal surface.
Skill and experience will often permit a fairly precise identification of the source of any specific fault, or at
least suggest the likely category in which it will be found. However, chemical analysis, Hull Cell tests, and
reliable service recommendations give the best foundation for successful troubleshooting. The most common
defects are listed here, together with their probable causes and some remedial steps.
Table A—Working Parameters of Single-Cell Trivalent Baths
Room Elevated
Temperature Temperature
Concentration of chromium, 15-25 15-25
g/liter 2.8-3.5 2.3-2.9
pH 20-22 27-44
Temperature, C 8-13 8-13
Current density. A/dm 2
50 1500+
Maximum thickness millionths Graphite Graphite
Anodes Indefinite Indefinite
Line of anodes Better than hexavalent Better than hexavalent
Throwing power and Covering Tolerant Tolerant
power Low levels of Cr3 Low levels of Cr3
Reaction to current None None
interruption Mild effect, similar to nickel Mild effect, similar to nickel
Effluent
Misting Microporous Microporous
Skin contact Microcracked Microcracked
4 millionth per minute 10 millionth per minute
Deposit structure Only to remove solids Only to remove solids
less than 25 millionth
greater than 25
Plating rate
Filtration
Milky Deposit
Possible Cause: Corrective Step:
High chromic acid/sulfuric Increase sulfate additions
ratio Remove chloride with silver carbonate
Chloride contamination Dilute bath
Iron contamination Clean anodes and reoxidize trivalent chromium
Excess trivalent chromium Carbon treat nickel to remove organic contamination, improve rinsing of
nickel and use a nickel activator
Poor nickel surface Reduce to normal, check control
High Temperature
Hazy Deposit
High chromic acid/sulfate Increase sulfate concentration
ratio Remove chloride with silver carbonate
High chloride Dilute bath
contamination Clean anodes and reoxidize trivalent chromium
Iron contamination Increase temperature to normal
Excess trivalent chromium Adjust anode-to-cathode ratio
Check electrical contacts
Low temperature Improve rinsing, use nickel activator
Current density too high
Intermittent current flow
Poor nickel surface
Gray and Dull But Smooth Deposits
ratio Reduce current
Current surge when contact Check temperature controllers
is made
High temperature
Dull Spots in High-Current-Density Areas
ratio Improving rinsing, use nickel activator
Passive nickel Use live entry to chromium bath
Bipolar condition
Blue Deposits
High temperature Reduce temperature to normal
Rough Deposits
Low sulfate Low Add sulfuric acid to increase
temperature Adjust temperature to normal
Surface preparation Improve cleaning and rinsing
Surface preparation Filter bath and eliminate source
Suspended particles in bath
Burned Deposits
ratio Add chromium salts
Low chromic acid Clean anodes and reoxidize trivalent chromium
Excess trivalent chromium Reduce current density or increase temperature
Increase temperature to normal; preheat large, cold parts
Too-high current density
Low temperature
Brown Spots or Rainbows
Low sulfate or catalyst Increase sulfate concentration; submit sample for analysis
Check racking, build-up on hooks and rack tips, contact on bus bars.
Inefficient contacts
Poor Adhesion
Insufficient etch Increase etch time; check etch bath
Surface contamination Improve rinsing and/or cleaning cycle
Intermittent contact Clean and check contacts; work should enter chromium bath live
Check surface preparation before nickel plating and condition of nickel bath
Poor nickel deposit
Poor Coverage
Low chromic acid content Add chromium salts
Low chromic acid/sulfate Precipitate excess sulfate with barium carbonate (See Table V)
ratio Raise current density
Clean contacts
Plating current too low Clean anodes
Oxidized contacts Reduce temperature to normal
Scaled anodes Activate nickle surface in nickel activator
High temperature
Passive nickel
Slow Deposition Rates

High chromic acid/sulfate Add the proper amount of sulfuric acid
ratio acid Increase voltage; check parts distribution; check for current leakage
Too-low current density Clean anodes
Clean contacts
Scaled anodes Increase rectifier size
Oxidized contacts Dilute bath
Insufficient power supply Follow procedure for the reoxidation of trivalent chromium
Iron contamination Reduce to normal temperature
Excess trivalent chromium
Too high temperature

Partial Deposition Rates

Too-low current density Increase voltage, clean rack contacts, clean anodes
Improve arrangement of parts on rack
Uneven current density Activate cathodically or immerse in hydrochloric acid 50 pct
Passive nickel Suspend parts so gas escapes freely
Gas pockets
No Deposit
Reverse polarity Make proper connections
Defective contacts Clean contacts
Excess sulfate Check ratio and correct
Chloride contamination Remove chloride with silver carbonate
Pitted Deposits
Pitted nickel deposit Filter nickel bath
Pitting in basis metal Improve basis metal preparation
Solution contamination Improve grinding and cleaning procedure
from
magnetic particles on Reposition work on racks to avoid gas formation
ground surfaces
Gas pitting
Table IV—Conversion of Excess Sulfate to Barium Carbonate Required

Bath Volume (gal)
Excess 100 200 300 400 500 600 700 800 900 1000
sulfate to be
removed Barium Carbonate Required (oz)
(oz/gal)
0.01 2.2 4.4 6.6 8.8 11.0 13.2 15.4 17.6 19.8 22.0
0.02 4.4 8.8 13.2 17.6 22.0 26.0 30.8 35.2 39.6 44.0
0.03 6.6 13.2 19.8 26.4 33.0 39.6 46.2 52.8 59.4 66.0
0.04 8.8 17.6 26.4 35.2 44.0 52.8 61.6 70.4 79.2 88.0
0.05 11.0 22.0 33.0 44.0 55.0 66.0 77.0 88.0 99.0 110.0
0.06 13.2 26.4 39.6 52.8 66.0 79.2 92.4 105.6 118.8 132.0
0.07 15.4 30.8 46.2 61.6 77.0 92.4 107.8 123.2 138.6 154.0
0.08 17.6 35.2 52.8 70.4 88.0 105.6 123.2 140.8 158.4 176.0
0.09 19.8 39.6 59.4 79.2 99.0 118.8 138.6 158.4 178.2 198.0
0.10 22.0 44.0 66.0 88.0 110.0 132.0 154.0 176.0 198.0 220.0
Note: 1 oz/gal = 7.5 g/liter

Table V—Conversion of Excess Sulfate to Barium Carbonate Required
Bath Volume (gal)
Excess sulfate 100 200 300 400 500 600 700 800 900 1000
to be removed
66° Bé Sulfuric Acid Required (fl oz)
(oz/gal)
0.01 0.05 1.0 1.6 3.1 2.1 4.2 2.6 5.2 3.1 6.3 3.7 7.3 4.2 8.4 4.7 9.4 5.2 10.4
0.02 1.0 1.6 2.1 4.7 6.3 6.3 8.4 7.8 9.6 10.9 12.5 14.1 15.7
0.03 2.1 2.6 3.1 7.8 9.6 10.4 10.4 12.5 14.6 16.7 18.8 20.9
0.04 3.1 3.7 4.2 10.9 12.5 13.0 15.6 18.2 20.9 23.5 26.1
0.05 4.2 4.7 5.2 12.5 14.6 15.6 18.8 21.9 25.0 28.2 31.3
0.06 5.2 6.3 14.1 16.7 18.2 21.9 25.6 29.2 32.9 36.5
0.07 7.3 15.7 18.8 20.9 25.0 29.2 33.4 37.6 41.8
0.08 8.4 20.9 23.5 28.2 32.9 37.6 42.3 47.0
0.09 9.4 26.1 31.3 36.5 41.8 47.0 52.2
0.10 10.4
Note: Fluid ounces × 29.5737 = cubic centimeters
Trivalent Chromium Oxidation. If anode deficiencies and bath contaminants (iron, copper, or other metal
ions, unstable mist suppressants, or stray parts corroding on the floor of the tank) allow the trivalent
chromium concentration (Cr+3) in the bath to exceed the recommended maximum of around two pct,
reoxidation is necessary.
Reoxidation of the Cr+3 requires that the bath be electrolyzed with clean (active) anodes, using an
anode/cathode area ratio of 30:1 and the highest bath temperature permissible. Occasionally the
electroplater can process loads of work using a high ratio of anode-to-cathode area to salvage his bath. More
often he will adopt one the three alternatives:
1. Periodic reoxidation of bath by electrolysis.
2. Continuous reoxidation of bath by means of a reoxidation cell within the plating tank.
3. Continuous reoxidation of the bath in a separate reoxidation tank.
Regardless of the method used, the reoxidation requires an anode current density of approximately 20 asf.
The cathode current density will then be about 600 asf, if the proper anode:cathode area ratio has been
maintained. Specific pointers on each of the three alternative procedures follow.
5. Cathode selector for use in reoxidation of trivalent chromium

When using tank anodes for the intermittent procedure, determine effective anode area for a pair of
anodes. For example, two anodes with 1.5 inches OD have an immersed length of 30 inches. The surface
area is 2 x 1.5 x 3.14 x 30 or 282.6 in.
To find the cathode length to use between the two tanks anodes, draw a line across from 282.6 in 2 to the
line showing the diameter of rod to be used. A 24-inch length of 1/8 inch OD rod should be used.
Chromium Plating
By Nabil Zaki
Vice President of Technology
MacDermid, Inc.
Kearny, New Jersey
Despite the simplicity of their formulations, chromium plating baths are more complicated to operate than
most plating baths, and they require rigorous controls.
CHROMIC-ACID-BASED BATHS (Hexavalent type)
In plating from hexavalent chromium baths, sulfate and fluoride ions act as catalysts. Temperature, current
density and bath composition affect the film characteristics and current efficiency. These parameters are
therefore carefully controlled in order to obtain specific deposit properties and plating rates.
Thicknesses of deposits vary from 0.25 to 0.5 micron (0.001 inch), or more for hard chromium plating.
Bath Composition
Chromic acid and sulfate are the necessary ingredients. Chromic-to-sulfate ratios range from 75:1 to 250:1.
The composition depends primarily on whether the bath is co-catalyzed, e.g. with fluorides, fluosili-cates or
fluoborates, and on the application (decorative or hard chromium).
Cr+6 is the source of chromium deposited from these baths. Chromic acid, Cr0 3, is the main component in
solution make-up. Cr+6 is reduced to Cr+3, which in turn is reduced to unstable Cr+2 and further to Cr0.
Some Cr+3 is normally found in operating baths, and indeed in the absence of Cr +3, little or no deposit is
obtained. The introduction of small amounts of reducing agents to a new solution helps in bath start-up.
An amount of Cr+3 exceeding two-three pct of the chromic acid content, however, reduces cathode
efficiency and causes a variety of plating problems.
The presence of other oxides of metals, e.g. iron, copper and nickel, combined with Cr +3, hurts bath
performance.
While the simple chromic-sulfate baths produce about 12 pct efficiency, co-catalyzed baths may deposit at
efficiencies up to 22 pct. For a given composition, there is an optimum range of current density and
temperature that produces a bright deposit. When a specific composition is found to produce the most
desirable results for a given application, it should then be tightly maintained by periodic analytical and
control methods.
Table I—Single Catalyst Plating Bath Parameters:
Chromic Acid 225-300 g/liter 250-400
Temperature 35-46C 49-65C (120-150F)
Current density 7.0-15 A/dm2 22-100 A/dm2
Co-Catalyzed and High-Speed

Baths Decorative Hard (heavy) plating
210-270 g/liter 200-300 g/liter
Chromic Acid 150:1 to 250:1 120:1 to 230:1
Chromic/Sulfate ratio 35-55C 43-55C
Temperature 7.0-15 A/dm2 22-90 A/dm2
Currently Density 10-16 pct 15-22 pct
Cathode efficiency
Typical single-catalyst and co-catalyst plating baths have the parameters shown in Table I.
In single-catalyst baths, cathode efficiency increases proportionally with chromic acid concentration, up to
250 g/ liter, and thereafter decreases (Fig. 1). Solutions with higher concentrations of chromic acid tolerate
a higher level of trivalent chromium and iron oxide contaminants. Additions of secondary catalyst improve
cathode efficiency at high concentrations of chromic acid, up to 300 g/liter.
Analyses of chromic acid (Cr+6), sulfate, secondary co-catalyst, e.g. fluoride, as well as trivalent chromium
(Cr+3) are needed to maintain the bath composition within the required limits.
Temperature
Chromium plated from trivalent solutions now has color closer to that of chromium from hexavalent
chromium solutions. (Photo courtesy Atotech USA, Rock Hill, SC)
Temperature is closely related to current density in its effect on brightness and coverage of deposit.
Generally, the higher the current density, the higher the temperature requirement (Fig. 2). An optimum
temperature range exists for a given concentration of chromic acid. Below or above that range, dull deposits
result.
In general, for decorative baths, the range is 35C (95F) to 46C (115F). For hard chromium, the range is 49C
(120F) to 65.5C (150F).
Since the chromic acid solutions used are fairly concentrated and viscous, stratification may occur. This
results in uneven temperature distribution within the solution. Agitation is therefore required to equalize
the bath temperature, to produce uniform brightness, and in the case of hard chromium, to improve deposit
hardness.
Preheating of parts to optimum bath temperature may be needed before they are introduced to the plating
tank, and in rare instances cooling of parts may be required, in order to insure uniformity of deposit. Using
both heating and cooling coils in the same tank may be necessary to maintain a precise temperature.
1. Effect of chromic acid concentration on current efficiency.
Current Density
At given solution composition and temperature, current density affects cathode efficiency, brightness and
hardness. Generally, the optimum current density is recommended by the manufacturer of the plating
chemicals used. At too-high current densities, burning or roughness of deposit occur. At low current
densities, lack of chromium coverage can be expected.
Be sure to use the proper current source. Deposit hazing and/or peeling can be traced to electrical
problems, especially in conventional chromic-sulfate (single catalyst) baths. Three-phase rectifiers with a
maximum of five pct AC ripple should supply an uninterrupted flow of current throughout the plating cycle.
Standard current densities are in the range of 7.75-15.5 A/dm 2 (0.5 to 1.0 asi) for decorative plating, and
23.25 to 100 A/dm2 (1.5 to 6.5 asi) for hard chromium plating.
Anodes Insoluble lead or lead-antimony alloy are used. Plating of inside diameters and recessed areas may
require that conforming anodes be fixtured at close proximity (0.5-1 inch) to the surface to be plated.
2. At constant temperature, cathode efficiency increases with current density. at constant current
density, cathode efficiency decreases with temperature.
In hard chromium plating, the closer the anode-to-cathode distance, the better the deposit distribution.
Lead anodes ideally should be 90 pct as long as the cathodes. Tops and bottoms should be slightly below and
above the tops and bottoms of the cathodes (parts) respectively to prevent excessive build-up at the plated
ends.
Properly operating lead anodes form a layer of dark brown lead oxide. A yellow or light colored coating on
the anodes indicates a build-up of lead chromate, which results from too little or no current flow, such as
during idle periods. This light colored layer has poor electrical conductivity.
Cleaning and reactivating lead anodes can be performed chemically, using cleaners specially formulated for
that purpose. Once cleaned, the anodes should be properly rinsed and promptly returned to the tank. A
satisfactory distribution of anodes consists of three anodes two inches in diameter or four 1.5-inch-diameter
anodes per foot of anode bar.
Self-Regulating High-Speed Baths
This type of solution incorporates fluoride complexes such as silicofluorides, in addition to sulfates. Salts of
low solubility are selected and used to release the desired anions on a controlled basis. Mixtures containing
potassium or sodium silicofluoride, and dichromate, for example, regulate the release of fluorides by
common-ion effect. Mixtures of strontium sulfate and chromate regulate the release of sulfate.
Consequently, at higher temperatures, the cathode current efficiency increases as a result of the increased
solubility of catalysts in this type of bath.
Crack-Free Chromium
This is deposited from baths with low catalyst ratio and high concentration of chromic acid. Since the
deposit is hard and brittle, it cracks when subjected to strain, forming a macro-cracked layer.
Micro-Cracked Chromium
Microcracking is produced by proprietary dual-catalyst baths. The micro discontinuity of the chromium layer
results in spreading the corrosion potential that exists between chromium and an underlying nickel plate.
This reduces the anodic current flowing to any one location on the nickel, greatly retarding the rate of
corrosion. Crack densities of 27-50 cracks per millimeter are specified for optimum corrosion resistance.
Microporous Chromium
3. Membrane separating anode box from cathode compartment in trivalent chromium plating.
Microporous chromium also improves the corrosion resistance of nickel-chromium deposits, in a manner
similar to that just described for microcracked chromium. Regular hexavalent chromium deposits are
typically made microporous by one of two different methods.
The bright nickel layer can be topped with another thin layer of nickel plated from a bath containing a very
fine suspension of inert particles, which codeposit with the nickel. Chromium plated over this layer deposits
around these particles, creating a microporous structure.
Another way to produce microporous chromium is to lightly spray the surface of the chromium deposit with
a hard, fine abrasive material such as 60- or 80-mesh alumina, or sand. The brittle chromium deposit breaks
at the point of impact, forming micropores and exposing the bright nickel layer beneath the chromium.
For best corrosion resistance, the pore density in both cases must exceed 10,000 pores per square
centimeter.
Cleaning and Surface Preparation
Inadequate cleaning of the basis metal will lead to poor plating results. In decorative plating, hazy, pitted or
non-adherent nickel deposits will be obtained as a result of inadequate surface preparation. The thin
chromium deposit will magnify and reflect these defects.
Table II—Comparison of Working Parameters of Trivalent Sulfate Type Versus Hexavalent Baths
Trivalent Hexavalent
Concentration of chromium g/liter 5-6 100-250
pH 3.5-3.9 0
Temperature (C) 40-50 40-50
Current density A/dm2 4-9 10-15
Anode:Shielded Anode Lead (alloy) Lead (alloy)
Anode:Insoluable Anode Composite metal oxides
Throwing power Good Poor
Reaction to current interruption Tolerant Causes "white wash"
Effluent Low level of Cr3 High level of Cr3
Skin contact Mild effect, similar to nickel Strong acid burn and ulceration
Deposit structure Microporous Induces microdiscontinuities
Plating rate 0.1 micron/min at 7 A/dm2 0.1 micron/min at 10 A/dm2
Allowing a nickel plated surface to dry during transfer will passivate the nickel and produce milky, hazy or
no deposit when chromium plated. In hard chromium plating, surfaces of the basis metal should be free of
oil, grease or rust.
Etching of steel and stainless steel insures proper adhesion. The extent of etch needed depends on the
composition of the steel. Carbon steel should be etched for 15-30 sec and up to 45 sec if the steel has been
heat treated. Etching is best performed in non-catalyzed solutions of 210-225 g/liter (28-30 oz/gal) chromic
acid to prevent overetching by sulfate, and particularly by fluoride catalysts.
Reverse etching in the same plating bath usually introduces an excessive amount of iron into the bath and
should be avoided.
4. Trivalent chromium can be plated from cell with shielded anode (left) or from single cell.
TRIVALENT CHROMIUM PLATING
Toxicity of Cr+6, low current efficiency, poor metal distribution, burns in high-current-density areas, "white-
wash" and lack of coverage around holes are some of the problems associated with Cr +6 plating baths. These
factors led to the eventual development of a safer and more efficient system, based on trivalent chromium.
Trivalent chromium plating baths for decorative applications enjoyed a steady, although initially slow,
acceptance as a substitute for hexavalent chromium plating. Their main attraction lies in the fact that they
eliminate many of the shortcomings of hexavalent chromium solutions.
Bath Chemistry
Several advances in technology have taken place, making the process more readily acceptable to platers.
Single-Cell Trivalent Chromium
A major distinction between trivalent chromium processes is the chemistry used to prevent the formation
of hexavalent chromium at the anode during plating. This must be done, since hexavalent chromium is a
poison to all trivalent chromium plating processes.
Fig. 4 shows the anode configurations of the shielded anode type and single-cell trivalent chromium
plating.
The single-cell process has built into its chemistry mechanisms to prevent the presence of hexavalent
chromium. No hexavalent can form at the anode, and if hexavalent chromium were added, the chemistry
of the single-cell bath would immediately convert the hex to
tri. This ability to convert hex to tri instantly permits continued deposition of chromium from the single-
cell bath.
The working parameters of the two available versions of the single-cell process are shown in Table A. The
room-tempera-ture process produces deposits similar in color to that of stainless steel or pewter. The
elevated-temperature produces
blue-white chromium almost identical in color to that from hexavalent baths. These solutions are more
sensitive to metallic impurities than hexavalent baths. The trivalent baths are easily purified.
Metallic impurities can be removed from single-cell baths by three methods. They can be plated out on
dummies. They can be removed quickly by adding a chemical purifier that precipitates large quantities of
metallic impurities at one time. Or they can be removed by ion exchange of a continuous basis. The
elevated-temperature single-cell process can produce deposits over 0.25 mil thick and maintain the
physical properties of hexavalent chromium deposits of similar thickness.
—Dr. Donald L. Snyder
World Wide Technical
Marketing Manager
Atotech USA
Cleveland, Ohio
There are currently at least three basic types of trivalent chromium baths available. A single electrolyte
bath, chloride or sulfate based, using graphite or composite anodes, and special additives to prevent
oxidation of trivalent chrome at the anodes (see accompanying "Single-Cell Trivalent Chrome" sidebar).
Another type, a sulfate-based system, uses shielded anodes. Conventional lead anodes are surrounded by
boxes sealed on one side by a selective ion membrane (Fig. 3, 4) and filled with dilute sulfuric acid.
The membrane used is a perfluorinated sulfonic acid, reinforced with an inert Teflon® fabric. The
membrane prevents the migrating trivalent chromium ions in the solution from reaching the anode, thus
preventing their oxidation to the hexavalent state.
The mechanism provides for excellent pH stability during plating. The bath is capable of producing light-
colored deposits very close to the appearance of deposits from hexavalent baths.
Table II summarizes the differences between Cr+6 and Cr+3 plating-bath parameters.
The sulfate type trivalent chromium solution is maintained as one would maintain a conventional bright
nickel bath. It utilizes a primary additive containing the trivalent chromium ion and a secondary additive
that contains grain refiners and brighteners. These materials are added on an ampere-hour basis, using
chemcial-feed pumps actuated by an ampere-hour meter.
Metallic impurities affect results as shown in Table III. These impurities can be plated out on dummies as
can be done with nickel baths, or through an external purification cell on a continuous basis. Ion exchange
columns can also be used, as well as precipitating agents followed by filtration.
A new insoluble catalytic anode has been developed for use in direct contact with the electrolyte of the
above sulfate-based system. The new anode is designed to maintain an electrode potential level that will
prevent oxidation of trivalent chrome at its surface. No selective oxidation additives are used in the
electrolyte. Consequently, the same high tolerance to metallic impurities, light colored deposits and pH
stability of this sulfate-based process are maintained. The users have a choice in selecting the shielded
anode or the insoluble direct contact type anodes with the same bath. This new development will make it
possible to use conforming and auxiliary anodes for plating of complex shaped configurations.
Deposit Characteristics
Trivalent chromium baths produce deposits that are inherently microdiscontinuous. Under about 0.65 micron
(25 millionths of an inch), trivalent chromium deposits are microporous. Typical density of the pores in a
microdiscontinuous deposit is 20,000 to 60,000 pores/sq cm. At higher thicknesses deposits are
microcracked.
The effect of microdiscontinuous chromium plating is to dissipate electrochemical corrosion current over a
wide surface area, thus improving corrosion resistance. Room-temperature and sulfate-type, trivalent
chromium processes plate at rates similar to those of hexavalent chromium baths—about 0.1 micron or four
millionths of an inch per minute. The elevated-temperature chloride process plates at about 0.25 microns or
10 millionths of an inch per minute. The hardness of the deposit is similar to that of traditional hexavalent
chromium—about 700 to 1,000 Vickers. Another advantage of the trivalent chromium bath is its ability to
tolerate current interruptions without passivating or production of white "clouds" and hazes in the deposit.
Stripping and replating over nickel can be carried out easily, with no adverse effects.
Comparison of Effluent Treatment for Cr+6 and Cr+3
As trivalent chromium plating baths contain no hexavalent chromium, effluent treatment of the subsequent
rinse waters is both simpler and cheaper. Most hexavalent chromium baths contain about 250 g/liter of
chromic acid, equivalent to 130 g/liter of chromium metal. Even if a dragout rinse is used, the running-
water rinses usually contain a high concentration of Cr +6.
Table III—Metallic Impurities and Their Effects on Trivalent Baths

Maximum Tolerance, mg/liter Effect
Metallic Impurity 500 Produced
Ni 30 If Exceeded
Cr (VI) 30 Darkening of deposit
Cu 70 Defects at low cd
Zn White blooms at high cd
Darkness at low cd
Effluent treatment consists of acidification of the rinse waters to obtain the required pH of 2.5, followed by
reduction of the Cr+6 to Cr+3, using sulfur dioxide or sodium bisulfite, according to the following equation:
CrO3 + 2 NaHSO3 + 2H2SO4
Cr2(SO4)3 + Na2SO4 + 3H2O
Finally the solution is neutralized and this causes precipitation of chromium hydroxide.
The theoretical requirement is three kilograms of sodium bisulfite (60-62 pct SO 2) plus two-three kilograms
of sulfuric acid to reduce one kg of hexavalent chromium. A trivalent chromium electrolyte may contain only
five g/liter of chromium and require only neutralization to achieve precipitation. On precipitation, the
volume of sludge generated by a hexavalent chromium electrolyte is approximately 30 times greater than
that from a trivalent bath.
A dilution of about 100 times with rinse waters might produce an effluent from the plating process of about
50 ppm (mg/liter), of Cr+3 before any further dilution occurs from other sources in the factory.
Hexavalent Chromium Plating Troubleshooting Guide
Common Plating Problems. Identifying the origin of a plating deficiency is the necessary first step in solving
the problem. The basic causes of poor plating usually fall into three categories:
• Faulty bath chemistry.
• Improper temperature and/or current density.
• Poorly finished and/or inadequately cleaned basis-metal surface.
Skill and experience will often permit a fairly precise identification of the source of any specific fault, or at
least suggest the likely category in which it will be found. However, chemical analysis, Hull Cell tests, and
reliable service recommendations give the best foundation for successful troubleshooting. The most common
defects are listed here, together with their probable causes and some remedial steps.
Table A—Working Parameters of Single-Cell Trivalent Baths
Room Elevated
Temperature Temperature
Concentration of chromium, g/liter 15-25 15-25
pH 2.8-3.5 2.3-2.9
Temperature, C 20-22 27-44
Current density. A/dm2 8-13 8-13
Maximum thickness millionths 50 1500+
Anodes Graphite Graphite
Line of anodes Indefinite Indefinite
Throwing power and Covering power Better than hexavalent Better than hexavalent
Reaction to current interruption Tolerant Tolerant
Effluent Low levels of Cr3 Low levels of Cr3
Misting None None
Skin contact Mild effect, similar to nickel Mild effect, similar to nickel
Deposit structure Microporous Microporous

less than 25 millionth Microcracked Microcracked
greater than 25 4 millionth per minute 10 millionth per minute
Plating rate Only to remove solids Only to remove solids
Filtration
Milky Deposit
High chromic acid/sulfuric ratio Increase sulfate additions
Iron contamination Dilute bath
Excess trivalent chromium Clean anodes and reoxidize trivalent chromium
Carbon treat nickel to remove organic contamination, improve
Poor nickel surface rinsing of nickel and use a nickel activator
Reduce to normal, check control
High Temperature
Hazy Deposit

High chromic acid/sulfate ratio Increase sulfate concentration
High chloride contamination Remove chloride with silver carbonate
Iron contamination Dilute bath
Low temperature Increase temperature to normal
Current density too high Adjust anode-to-cathode ratio
Intermittent current flow Check electrical contacts
Poor nickel surface Improve rinsing, use nickel activator
Gray and Dull But Smooth Deposits
Current surge when contact is made Reduce current
High temperature Check temperature controllers
Dull Spots in High-Current-Density Areas
Passive nickel Improving rinsing, use nickel activator
Bipolar condition Use live entry to chromium bath
Blue Deposits
High temperature Reduce temperature to normal
Rough Deposits
Low sulfate Low temperature Add sulfuric acid to increase
Surface preparation Adjust temperature to normal
Surface preparation Improve cleaning and rinsing
Suspended particles in bath Filter bath and eliminate source
Burned Deposits

Low chromic acid Add chromium salts
Reduce current density or increase temperature
Too-high current density Increase temperature to normal; preheat large, cold parts
Low temperature
Brown Spots or Rainbows

Low sulfate or catalyst Increase sulfate concentration; submit sample for analysis
Check racking, build-up on hooks and rack tips, contact on bus
Inefficient contacts bars.
Poor Adhesion

Insufficient etch Increase etch time; check etch bath
Surface contamination Improve rinsing and/or cleaning cycle
Intermittent contact Clean and check contacts; work should enter chromium bath live
Check surface preparation before nickel plating and condition of
Poor nickel deposit nickel bath
Poor Coverage
Low chromic acid content Add chromium salts
Low chromic acid/sulfate Precipitate excess sulfate with barium carbonate (See Table V)
ratio Raise current density
Clean contacts
Plating current too low Clean anodes
Oxidized contacts Reduce temperature to normal
Scaled anodes Activate nickle surface in nickel activator
High temperature
Passive nickel
Slow Deposition Rates
High chromic acid/sulfate Add the proper amount of sulfuric acid
ratio acid Increase voltage; check parts distribution; check for current leakage
Too-low current density Clean anodes
Clean contacts
Scaled anodes Increase rectifier size
Oxidized contacts Dilute bath
Insufficient power supply Follow procedure for the reoxidation of trivalent chromium
Iron contamination Reduce to normal temperature
Excess trivalent chromium
Too high temperature

Partial Deposition Rates
Too-low current density Increase voltage, clean rack contacts, clean anodes
Improve arrangement of parts on rack
Uneven current density Activate cathodically or immerse in hydrochloric acid 50 pct
Passive nickel Suspend parts so gas escapes freely
Gas pockets
No Deposit
Reverse polarity Make proper connections
Defective contacts Clean contacts
Excess sulfate Check ratio and correct
Pitted Deposits
Pitted nickel deposit Filter nickel bath
Pitting in basis metal Improve basis metal preparation
Solution contamination from Improve grinding and cleaning procedure
magnetic particles on
ground surfaces Reposition work on racks to avoid gas formation
Gas pitting
Table IV—Conversion of Excess Sulfate to Barium Carbonate Required

Bath Volume (gal)
100 200 300 400 500 600 700 800 900 1000
Excess sulfate Barium Carbonate Required (oz)

to be
removed
(oz/gal)
0.01 2.2 4.4 6.6 8.8 11.0 13.2 15.4 17.6 19.8 22.0
0.02 4.4 8.8 13.2 17.6 22.0 26.0 30.8 35.2 39.6 44.0
0.03 6.6 13.2 19.8 26.4 33.0 39.6 46.2 52.8 59.4 66.0
0.04 8.8 17.6 26.4 35.2 44.0 52.8 61.6 70.4 79.2 88.0
0.05 11.0 22.0 33.0 44.0 55.0 66.0 77.0 88.0 99.0 110.0
0.06 13.2 26.4 39.6 52.8 66.0 79.2 92.4 105.6 118.8 132.0
0.07 15.4 30.8 46.2 61.6 77.0 92.4 107.8 123.2 138.6 154.0
0.08 17.6 35.2 52.8 70.4 88.0 105.6 123.2 140.8 158.4 176.0
0.09 19.8 39.6 59.4 79.2 99.0 118.8 138.6 158.4 178.2 198.0
0.10 22.0 44.0 66.0 88.0 110.0 132.0 154.0 176.0 198.0 220.0
Note: 1 oz/gal = 7.5 g/liter
Table V—Conversion of Excess Sulfate to Barium Carbonate Required

Bath Volume (gal)
100 200 300 400 500 600 700 800 900 1000
Excess 66° Bé Sulfuric Acid Required (fl oz)
sulfate to be
removed
(oz/gal)
0.01 0.05 1.0 1.6 3.1 2.1 4.2 2.6 5.2 3.1 6.3 3.7 7.3 4.2 8.4 4.7 9.4 5.2
0.02 1.0 1.6 2.1 4.7 6.3 6.3 8.4 7.8 9.6 10.9 12.5 14.1 10.4
0.03 2.1 2.6 3.1 7.8 9.6 10.4 10.4 12.5 14.6 16.7 18.8 15.7
0.04 3.1 3.7 4.2 10.9 12.5 13.0 15.6 18.2 20.9 23.5 20.9
0.05 4.2 4.7 5.2 12.5 14.6 15.6 18.8 21.9 25.0 28.2 26.1
0.06 5.2 6.3 14.1 16.7 18.2 21.9 25.6 29.2 32.9 31.3
0.07 7.3 15.7 18.8 20.9 25.0 29.2 33.4 37.6 36.5
0.08 8.4 20.9 23.5 28.2 32.9 37.6 42.3 41.8
0.09 9.4 26.1 31.3 36.5 41.8 47.0 47.0
0.10 10.4 52.2
Note: Fluid ounces × 29.5737 = cubic centimeters
Trivalent Chromium Oxidation. If anode deficiencies and bath contaminants (iron, copper, or other metal
ions, unstable mist suppressants, or stray parts corroding on the floor of the tank) allow the trivalent
chromium concentration (Cr+3) in the bath to exceed the recommended maximum of around two pct,
reoxidation is necessary.
Reoxidation of the Cr+3 requires that the bath be electrolyzed with clean (active) anodes, using an
anode/cathode area ratio of 30:1 and the highest bath temperature permissible. Occasionally the
electroplater can process loads of work using a high ratio of anode-to-cathode area to salvage his bath. More
often he will adopt one the three alternatives:
1. Periodic reoxidation of bath by electrolysis.
2. Continuous reoxidation of bath by means of a reoxidation cell within the plating tank.
3. Continuous reoxidation of the bath in a separate reoxidation tank.
Regardless of the method used, the reoxidation requires an anode current density of approximately 20 asf.
The cathode current density will then be about 600 asf, if the proper anode:cathode area ratio has been
maintained. Specific pointers on each of the three alternative procedures follow.
5. Cathode selector for use in reoxidation of trivalent chromium.

When using tank anodes for the intermittent procedure, determine effective anode area for a pair of
anodes. For example, two anodes with 1.5 inches OD have an immersed length of 30 inches. The surface
area is 2 x 1.5 x 3.14 x 30 or 282.6 in.
To find the cathode length to use between the two tanks anodes, draw a line across from 282.6 in 2 to the
line showing the diameter of rod to be used. A 24-inch length of 1/8 inch OD rod should be used.
Periodic Reoxidation of Bath. Raise the plating-bath temperature to at least 145F, or to the highest
temperature permis-sible for the tank-lining material, and space the tank anodes evenly along the anode
bar. Position a small-diameter cathode rod (copper) between each pair of anodes. The diameter/length
relationship of the cathode rods should relate to the effective anode area as indicated in Fig. 5. In the event
the cathode is not of the same length as the anodes, the indicated length to be plated should be centrally
positioned. If necessary, mask or tape the top section to permit proper positioning.
Electrolyze the chromium plating bath until the Cr +3 concentration is down to about one pct of the chromic
acid concentration. The duration of the bath electrolysis will depend on the initial Cr +3 concentration, the
total anode area available for the particular bath volume, and the temperature of the bath. The efficiency
of oxidation will decline as the Cr+3 concentration drops. For example, less electrolysis will be needed to
lower the trivalent chromium level from five pct to four pct than to reduce it from two pct to one pct.
It may be necessary to electrolyze the bath for several overnight periods or over a weekend to lower the Cr +3
concentration to the desired level (one pct of the chromic acid present). If the current/volume ratio is five
A/gal of solution, the anode current density 20 asf, and the cathode current density 600 asf, it will take
about two hours of electrolysis (on the average) to reduce the Cr+3 concentration 0.1 oz/gal. PFD
REFERENCES
Dennis, J.K. and Such, T.E., Nickel and Chromium Plating, Butterworth Publishers, 1986.
Canning, Handbook on Electroplating, 22nd edition, 1978. Salauze, J., Traite'De Galvanoplastic, 2nd
edition, 1950.
Zaki, N., "Advances in Trivalent Chrome Plating," AESF Chromium Colloquium, 1987.
Chromium Plating
An overview of decorative and hard chromium electroplating processes
By Chrissy Bieler
MacDermid Inc.

Chromium plating continues to be the coating of choice for many metal finishing applications. Demand for
chrome's bright and lustrous finish continues to grow despite competition from other finishes such as organic
coatings and vapor deposition. Chromium has withstood the competitive challenges due to its unmatched
aesthetics as well as its superior technical capabilities including exceptional corrosion performance, multi-
substrate capability and supply chain factors such as industrial scale, extensive installed applicator base and
long application history and experience. Chromium is widely used in the metal finishing industry for both
decorative and hard chrome plating.
Chromium plating has been carried out on a commercial basis since 1924. In decorative applications the
chrome is plated as a thin (0.25-0.8µm) layer over nickel to provide an economical and highly corrosion
resistant deposit. Most decorative chromium deposits are produced using hexavalent chromium electrolytes.
In the last decade processes based on trivalent chromium have gained increasing acceptance in the industry.
Staples Center
Bright chromium can be applied as continuous (regular) or discontinuous layers. Discontinuous deposits are
formed by depositing the chromium on microporous (or microcracked) nickel plate. The selection of a
continuous or discontinuous layer depends on the level of corrosion resistance required. Failure of bright
chromium plate is often due to deep pits developing as a result of corrosion starting at random cracks or
pores in the chromium surface. Corrosion is an electrochemical mechanism. Because these cracks or pores
are relatively widely spaced, the current developed by the chromium/nickel couple is concentrated at a few
points. Deep pits form at these points and rapidly penetrate through the nickel deposit and the component
substrate. Inducing micro-discontinuities (microcracks) across the surface spreads the corrosion current and
slows the corrosion rate.Typically, articles plated to service condition 1/2 would use regular chromium
plate, whereas plating to service condition 3 or above would use a discontinuous layer (ASTM B456).
Decorative Hex Electrolytes

Four types of hexavalent chromium electrolytes are commonly employed: sulfate- only catalysts, sulfate-
fluoride catalysts, sulfate-fluoride-organic catalysts and self- regulating high speed (SRHS). The primary
differences between the systems are outlined in Table I.
The most common electrolytes employed today are based on the dual sulfate/fluoride catalyst. This mixed
catalyst has the advantages of improving cathode efficiency, covering power and ability to plate on bright
nickel layers when compared to the straight sulfate catalyst type.
Over the last decade the popularity of the triple catalyst system has grown. This system has characteristics
similar to the dual catalyst with advantages of higher cathode efficiencies, wider operating window and
improved covering power. To operate these systems, regular analysis of the chromic acid, sulfuric acid and
proprietary catalysts concentrations are required.
In markets where access to regular analytical control is limited, the use of SRHS chemistries continues.
These systems regulate the active sulfate and catalyst levels ratio to chromic acid by use of proprietary
solubilizing agents.
Hexavalent chromium plating solutions have poor deposit distribution. Therefore, when plating to
specification, it is necessary to calculate the plating time based on minimum thicknesses required on
significant surfaces. A major factor in plating time is the cathode efficiency of chromium plating solutions,
which is influenced by the following factors:
Type of electrolyte. This is outlined in Table I. Solutions with higher cathode efficiencies have improved
throwing and covering power than the simpler electrolytes. The ability to cover components more evenly is
one factor that has led to the popularity of triple catalyst systems.
Solution concentration. The cathode efficiency of a solution rises as chromic acid concentration rises until it
reaches a peak at about 250 g/L; thereafter, any increase in concentration lowers cathode efficiency. High-
concentration solutions are, however, simpler to control than those of low concentration, are less affected
by small changes in sulfate content and will operate with a higher oxide content.
Current density employed. Cathode efficiency varies directly with current density. The higher the current
density, the greater the cathode efficiency.
Solution temperature. Cathode efficiency falls with increasing temperature. Higher operating temperatures
do, however, permit use of higher current densities. In practice, the optimum temperature is related to the
current density employed. With self-regulating solutions, a rise in temperature results in a slight rise in
cathode efficiency.
Solution composition. Cathode efficiency is also affected by the oxides that is, trivalent chromium content
and contaminations such as iron and nickel. Solution efficiency drops as these constituents build up in the
solution. Cathode efficiency is also reduced if the solution is out of balance, for example, when addition
agents, etc. are lower than the optimum.
Staples Center
Calculation of Plating Times

Any change in current density will generally involve a corresponding adjustment in temperature to keep the
solution within the optimum plating range. These changes will also affect cathode efficiency. Table II shows
the time needed to produce a deposit averaging 1 µm in thickness at various cathode efficiencies and
current densities. These plating times are for average thickness values under uniform current density
conditions. In practice there will be considerable variation in current density over the surface and,
therefore, the average thickness of chromium applied will be in excess of any minimum thickness
requirements.
Equipment and anodes. Chromium plating solutions are usually contained in PVC-lined tanks. The solution is
heated by means of either silica-cased or Teflon electric immersion heaters or steam coils. Tin-lead alloy
anodes are generally employed for chromium plating. In a chromium plating tank the lead anodes serve two
purposes: as the positive electrode and to maintain the solution in satisfactory balance by re-oxidizing the
trivalent chromium to chromic acid. The anode area should be about 20% greater than the area of the
normal plating load. When current is passing through the chrome solution gassing will occur at the anodes,
which are normally covered with a dark chocolate colored film. This film is necessary to ensure that the
trivalent chromium produced by electrochemical reduction of the chromium acid at the cathode is re-
oxidized to ensure correct solution balance.
Spray control. During electrolysis of the chromic acid, a mist is produced which must be controlled by the
use of a suitable chemical mist suppressant, usually in conjunction with local exhaust ventilation. The U.S.
Occupational Safety and Health Administration (OSHA) standard for the permissible exposure limit (PEL) for
chromic acid mist is 5 µg/m3 with an action level at 2.5 µg/m3. Proprietary chemical mist suppressants are
usually based on perfluoro-octane sulfonates (PFOS). However, these materials are themselves becoming
subject to prohibition due to their environmental persistence and bio-accumulative effects in mammals.
New, PFOS-free materials which will break down in use are now being introduced to address this
requirement.
Solution maintenance. Chromium plating solutions are regularly analyzed for chromic acid, sulfates, catalyst
and contamination. Deficiency in chromic acid concentration is restored by the use of a proprietary salt
mixture which restores the balance of the solution catalysts at the same time. Deficiency in sulfate is
restored by sulfuric acid. If the sulfates are too high due to drag-in from the prior nickel plating stage, the
level is reduced by addition of either barium carbonate or hydroxide.
For correct operation, a small proportion of the chromium (1-3 g/L) must be present in the solution as the
trivalent radical. Above this level the efficiency of the solution may fall and show narrower bright chromium
plating. Over time, metallic contamination such as iron, copper or nickel will build up in solution. These
heavy metals are often analytically estimated collectively as â€œoxidesâ€ (Cr2O3, Fe2O3, and so on).
Total oxides should not be allowed to rise above 5% of the total hexavalent concentration.
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Decorative Trivalent Electrolytes

Trivalent chromium plating solutions have become an increasingly popular alternative in the metal finishing
industry for a variety of reasons, including increased cathode efficiency and throwing power in addition to
lower toxicity. The total chromium metal concentration used in a trivalent chromium solution is significantly
lower than that of a hexavalent plating solution—<3 oz/gal, versus 15-20 oz/gal for hexavalent solutions.
This reduction in metal concentration, in addition to the lower viscosity of the solution, leads to less
dragout and wastewater treatment and therefore a cost reduction in the plating process. Trivalent
chromium baths, as a result of their excellent throwing power, also produce less rejects and allow for
increased rack densities in comparison to hexavalent chromium. While trivalent chromium plating has a
number of advantagesolution, the system also has some drawbacks. Specifically, the color of trivalent
chromium deposits and the decreased plating rate in comparison to hexavalent chromium pose potential
difficulty in their implementation.
Historically, the color of trivalent chromium deposits was darker than that of hexavalent chromium. While
this problem has been greatly reduced there still exists some slight color difference between the two
finishes.The slower plating rate of trivalent chromium baths has also prevented platers from
switching.Development of a trivalent chromium plating solution that could overcome both of these
weaknesses is ongoing and crucial if trivalent chromium is to be considered a valid alternative to hexavalent
chromium.
Just as different electrolyte options exist for hexavalent chromium plating so do similar choices exist for
plating trivalent chromium. Trivalent chromium processes utilize either a sulfate or chloride-based
electrolyte. A comparison of these systems can be seen in Table III.
Sulfate-based systems are more beneficial than chloride for a variety of reasons.The deposit is of a higher
purity with these systems, which leads to better corrosion protection and a color closer to that of
hexavalent chromium. The chemistry of sulfate-based systems is also less corrosive, which prevents
deterioration of the plating environment and unplated component areas. The solution is also easier to
control and the additives can easily be analyzed. Finally, the solution does not complex the metals in
solution, which allows their removal by purification or low-current-density dummying.
Equipment and solution maintenance. Trivalent chromium plating solutions operate with equipment similar
to that used with hexavalent chromium chemistries. In the event that a plating tank is to be converted from
hexavalent to trivalent, all new equipment should be installed to ensure that no contamination of the
trivalent chromium solution will occur.
Trivalent chromium solutions should be installed in tanks lined with either PVC or polypropylene. Titanium
coils, or titanium-clad, silica-cased, or Teflon electric immersion heaters should be used. Continuous
filtration is recommended, and carbon (graphite) or coated titanium anodes are required depending on the
chemistry.
Plating bath analysis involves regular assessment of the chromium, conductivity salt and complexor
concentrations as well as pH and specific gravity. Ampere-hour dosing of the replenishment components can
be utilized for easier operation.
Dark trivalent coatings. Dark coatings are becoming ever more popular in the industry today. The
appearance of a dark and shiny finish that can withstand the testing criteria of hexavalent chromium is
desired for many applications, and dark trivalent chromium solutions exist that meet both appearance and
technical requirements. These solutions exhibit excellent covering and throwing power, consistent color at a
wide range of current densities and the advantage of low-metal operation in comparison to hexavalent
chromium. These coatings are capable of exceeding 96 hr of Copper-accelerated acetic acid salt spray with
no notable change to deposit appearance.
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Hard Chrome Plating

Hard chrome plating is normally described as the application of an electroplated chrome deposit with a
thickness of greater than 0.0002 inch. Hard chrome deposits are normally plated to a thickness of 0.0005-
0.01 inch, although in theory almost unlimited thicknesses can be achieved.
Commercial hard chromium plating started in the late 1920s to the early 1930s after work in both the U.S.
and Germany using a bath based on chromic and sulfuric acids at a ratio of 100:1. In the intervening years
the basic formulation of the electroplating bath for hard chrome plating has not altered, and although there
have been improvements made to the technology a lot of electroplaters still use this original chemistry.
The reason for the growth of hard chrome plating into the multimillion dollar business it is today is that the
chrome deposit from these solutions has combination of properties which has not been matched by any of
the later technologies offered and tested. These properties include:
* High hardness

* Low coefficient of friction
* Excellent wear resistance
* Excellent corrosion resistance (especially in oxidizing atmospheres). Hard chrome can be applied at a
very low cost compared to alternatives, and it can plate on a wide variety of substrates. This explains why,
despite environmental issues, hard chrome continues to be widely specified and used..
The ability to electroplate chrome metal from a hexavalent chrome solution theoretically is not possible;
however, it is achieved by using an acid radical as a catalyst. This catalyst has historically been sulfate,
although others such as fluoride can also be used.
Types of Hard Chrome. There are three main types of hard chrome in operation. The properties of these
systems are given in Table IV. The plating rate of each type of solution depends on the current density and
efficiency of the plating solution.
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Sargeant solution consists of chromic acid and sulfate at a ratio of about 100:1. This bath is often offered as
a self-regulated process where the controlled solubility of a chosen sulfate compound is used to maintain
the correct ratio in the solution. These baths are cheap to run, but have low cathode efficiency and give
lower hardness and generally worse corrosion protection than more modern systems.
Fluoride-catalyzed processes are used with sulfate. TThey give a much harder as-plated deposit and have
much higher cathode efficiency than Sargeant solution, and thus have a higher plating rate. the dow side is
that their chemistry is much more aggressive to both equipment and the plated parts, hence metallic
contamination is a serious issue. This has limited their use although they have found some specific
applications where they are used extensively.
Organic acid salts can also be used in conjunction with sulfate in the chrome solutions and have become, for
most, the preferred option. They have high efficiency, plate very hard deposits and due to the high level of
micro-cracking found with these systems they offer good corrosion protection. Some of the earlier systems
used have a negative effect on the rate of anode corrosion, but more modern chemistries show similar
anode corrosion to the early Sargeant processes.
Equipment. Tanks for hard chrome plating solutions should be used in tanks lined with a flexible polyvinyl
chloride. Koroseal is a typical example of this. Lead-lined tanks are not recommended.
Any required heating or cooling equipment should be constructed of PTFE or a similar fluorocarbon,
tantalum or titanium; although use of titanium is not recommended if using a fluoride catalyzed process.
The power used for hard chrome plating should have a smoothed wave, because ripple can cause many
technical issues in a hard chrome solution. Power supplies should be capable of up to 15 V for normal
applications. Because large currents and voltages are used, the bus bars should be capable of carrying the
current required without overheating. It is also important to insulate all conducting materials from external
power to reduce the risk of stray currents being formed.
Carbide Efficiency
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Carbide Efficiency
For most systems, the use of tin-lead anodes (7% Sn) is recommended. The anode area should be about 150%
of the cathode area to reduce the risk of an increase in the trivalent chrome concentration.
In some circumstances lead/antimony anodes are used, as these are more rigid than tin/lead and so are less
likely to stretch in larger tanks. These anodes should not be used with fluoride-based systems, because they
corrode more quickly and have a lower conductivity than traditional tin/lead anodes.
In some countries platinum-coated titanium anodes are increasingly being used. These cost substantially
more initially but often save money, as they can last up to 10 years and they do not generate lead chromate
sludge that can be difficult to remove. It is important when using these anodes to maintain a small amount
of lead in the solution; without this, the trivalent chrome concentration can increase leading to quality
issues.
Due to the poor throwing power of hard chrome plating solutions, the use of auxiliary anodes and shields is
common, and is one of the major skills required by hard chrome electroplaters.
Extraction equipment is needed because hard chrome plating is very inefficient electrochemically and
generates a considerable amount of hydrogen gas at the cathode. This can give a very heavy â€œmistâ€
from the plating solution. As previously mentioned, permissible exposure limits have recently been reduced
and are very low. For this reason it is very important to provide excellent extraction. It is also possible to
use surfactants to reduce the surface tension of the plating tank.
Operation. The operation of a hard chrome solution is not complex, but there are certain aspects that must
becontrolled. These are: chromic acid concentration, sulfate concentration, catalyst concentration (if using
more than sulfate), temperature and metallic oxide contamination such as iron, nickel copper or trivalent
chrome; this is important in ensuring the best efficiency from the plating solution (see the section on
contamination).
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Substrates. It is possible to plate most substrates in hard chrome by altering the pretreatment used.
Substrates commonly plated include steel, hardened steel, cast iron, bronze (used as an undercoat to give
corrosion protection) and aluminum. It is advantageous to use a fluoride-catalyzed bath when plating on
hardened steels or nickel alloys if immersion or anodic activation is being used, but it is possible to plate
these in the other catalyzed systems using separate activation and a cathodic wash.
It is also possible to plate hard chrome onto previously plated hard chrome or other plated finishes. One of
these is electroless nickel, where a combination of the hard chrome wear and hardness with the even
thickness of the EN can provide many advantages.
Contamination. All chrome solutions build up in contaminants, and it is important to minimize these as they
have a negative effect on the quality of the plating. This is more true with hard chrome plating than
decorative chrome, as there is minimal drag-out in hard chrome and thus contaminants tend to increase
faster in these solutions.
As cations build up in the plating solution, they reduce the conductivity of the solution leading to an
increase in the voltage required to maintain a current density and a potential loss of efficiency.
It is possible to remove metallic contamination by using a porous pot technology, electrodialysis or ion
exchange. Ion exchange has to be used with a dilute solution to avoid attack on the resin, so it is more
commonly used to purify the drag out solution which can then be added back to the plating tank.
Properties. Hard chrome offers a hard, lubricious, corrosion-resistant and wear-resistant coating. One of the
main reasons for its good performance in corrosion testing is that the deposit is micro-cracked; if the
deposit is thick enough (normally >1 mil) the cracks in the deposit do not reach the substrate and corrosion
performance is markedly improved.
Macro-cracks, on the other hand, can result in accelerated corrosion. Generally if a deposit is macro-
cracked it is neither as hard nor as wear resistant as a micro-cracked process. Micro cracking also is
advantageous in lubricated applications, as the lubricant is stored in the cracks. Table V gives a summary of
some of the performance characteristics of hard chrome deposits.
Decorative and Hard Chromium Electroplating
A comparison of hexavalent and trivalent processes, chemistries, process and operating parameters,
deposit properties and equipment
By Allen R. Jones and Donald Snyder
Atotech USA Inc.
Rock Hill, SC
The electrodeposition of chromium has been used since the mid 1800s because of the
depositâ€™s unique combination of properties that hasn't been matched by any other single
material. Commercially, chromium deposits are typically divided into two groups, decorative
and hard (functional) chromiumâ€”based more on their applications than on the chemistry of the processes.
Decorative Chromium Plating
Decorative chromium electrodeposits, â€œchrome,â€ are almost exclusively used as protective topcoats
for decorative parts. Many of the parts are fabricated from the least expensive and easiest to form material
(substrate) that offers the required physical properties. Typical chrome substrates are nickel or copper plus
nickel-plated plastic, steel, zinc die-castings and aluminum. Stainless steel is one of the few substrates
frequently plated directly with decorative chromium as well as with nickel and then chromium. Once
plated, all of the parts produced from the different substrates have the same consistent, eye-appealing,
metallic looking decorative chrome appearance.
Decorative chromium is usually plated in the thickness range of 0.2â€“0.5 Î¼m. Even though the deposits
are very thin, they offer the physical and chemical properties that are required for most decorative parts.
Thinner deposits are very porous and offer minimal physical properties. Thicker deposits tend to be dull and
form visible cracks. The service life of chrome-plated parts can vary from untouched ceiling light fixtures in
environmentally controlled rooms to truck bumpers and wheels traveling thousands of miles per year with
minimal cleaning or other care. The depositâ€™s appearance is retained in service because of its hardness
and its excellent tarnish (surface corrosion), wear, chemical and scratch resistance
However, all of these properties depend on the chromium deposit interacting in synergy with its underlying
deposit, typically nickel. Bright nickel deposits help give the chromium deposit its bluish-white color and the
chromium deposits protect the nickel from dulling due to surface oxidation. While multiple or single layers
of nickel are primarily responsible for protecting the substrate from corrosion, the chromium deposit helps
control the corrosion rate and is responsible for maintaining the overall reflective decorative appearance
during service. Nickel and especially copper plus nickel also improve the appearance of the part by leveling
out the defects (scratches, pores, etc.) in the substrate. This reduces the need for expensive surface
preparation of the substrate.
Hexavalent Chromium
Hexavalent or trivalent chromium electrolyte can be used to electroplate decorative chromium. Hexavalent
chromium use is
being increasingly regulated for environmental and worker safety reasons. Hexavalent chromium ions are
carcinogenic and
strong oxidizers while trivalent chromium ions are neither. Also, hexavalent processes are highly acidic
while trivalent are mildly acidic. Hexavalent chromium processes produce the blue-white deposit that is
considered the standard for the appearance of chrome.
Trivalent Chromium
Trivalent chromium processes can produce deposits that vary from an almost hexavalent chromium deposit
appearance,
metallic white, to a pewter/stainless steel appearing deposit that appears to have depth. In almost all
cases, the physical properties of trivalent chromium deposits are equivalent to those of micro-discontinuous
(micro-pores or micro-cracks invisible without magnification) hexavalent chromium deposits. 1 Decorative
trivalent chromium deposits are microporous
as plated while pre- or post-treatments are used to produce micro-discontinuous hexavalent chromium
deposits
Compared to chromium deposits without micro-discontinuities, micro-discontinuous chromium deposits over

electroplated nickel significantly enhance the protection of the part from substrate corrosion. Hexavalent
chromium deposits are not plated with sufficient micro-sized pores or cracks to offer this protection. One
method to increase the micro-pore count is to lightly spray the dried nickel plus chromium plated part with
hard particles such as aluminum oxide. This cracks the brittle chromium deposit and produces micro-porous
chromium. A more frequently used method is to deposit a customized nickel strike in between the bright
nickel and the chromium deposits. If inert particles are codeposited within this nickel strike (particle nickel
deposit), the subsequent chromium deposit will contain micro-pores where the chromium does not plate
over the exposed particles. Another far less common approach is to use a nickel strike that is designed to
micro-crack after being chromium plated. This micro-cracks the chromium deposit. An even less frequently
used method is a specially designed hexavalent chromium process that forms micro-cracks during plating.
Control of this process is difficult. Trivalent chromium deposits under 0.5 microns thick are micro-porous as
plated. Thicker deposits are micro-cracked.
Micro-discontinuities in the chromium deposit spread the corrosion potential over the chromium and
underlying nickel deposits, with the chromium the cathode and the nickel exposed through the micro-
discontinuous sites, the anode. Because of the very large number of nickel sites, the anode current at any
one location on the nickel is greatly reduced, which retards the rate of corrosion at any one site. North
American automotive decorative chromium specifications require nickel plus micro-porous chromium for all
exterior applications because of its increased corrosion resistance while maintaining the after-corrosion
appearance of the chromium deposit. These specifications do not allow micro-cracked chromium deposits
but they are permissible in other areas of the world. The importance of microdiscontinuous chromium and
the required physical properties of the underlying nickel deposits are reviewed in ASTM B 456, which
specifies a minimum of 30 micro-cracks per mm or 10,000 micro-pores per sq cm. 2
Decorative Chemistries
There are several different families of decorative chromium processes, each offering specific advantages.
They are extremely versatile, which blends the properties of one process into the advantages of another
process. However, a plater may prefer one process compared with another because it offers advantages for
his particular operation. Decorative chromium processes are most easily divided based upon their catalyst
system, as shown in Table I. Chromium trioxide, CrO3 , commonly referred to as chromic acid (the hydrated
form of CrO3 ) is used to supply the hexavalent chromium
ions. The sulfate is commonly controlled byaddition of sulfuric acid (H 2 SO4 ). Proprietary additives are
usually used to control the fluoride catalyst. Proprietary trivalent chromium processes are used in almost all
cases because of the complexity of the solution formulation.
The hexavalent chromium processes listed in Table I can be further divided into self-regulating processes
and those regulated by analysis. Self-regulating processes use additives that dissolve at the level required to
maintain the proper catalyst concentration for the process. Increased temperatures raise catalyst levels
resulting in improved plating rates. The analytically controlled processes use soluble additives that contain a
specific amount of catalyst. Catalyst adds based upon analysis or amp-hours offer the advantage of varying
their concentration to alter the bath performance
Some of the advantages and disadvantages of hexavalent and trivalent chromium processes are listed in
Table II. Other than the type and amount of catalysts used, most hexavalent chromium processes have
similar operating conditions (Table III). This table also contains some general operating conditions for
trivalent chromium processes. Some of the more specific factors within each process family also can be
listed.
Single-Catalyst Hexavalent Processes. All chromium processes use less than 100% of their cathode
efficiencies for chromium deposition. Single-catalyst processes have about 12% chromium plating efficiency.
The remaining current goes to the formation of hydrogen and trivalent chromium, Cr 3+ . The chromium
deposition effi ciency increases proportionally with chromic acid concentration, up to 250 g/l and decreases
thereafter. A CrO3 /SO4 ratio of approximately 100:1 is common. Chloride in any hexavalent chromium
process will over catalyze the process and adversely affect the appearance of the deposit.
Co-catalyzed Hexavalent Processes. The inclusion of the second catalyst, fluoride, can increase the
average cathode efficiency to about 22%. The efficiency increases with increasing chromic acid
concentration up to 300 g/liter. A CrO 3 /SO4 ratio of about 190:1 is common. These processes are less
sensitive to current interruptions and can plate over more passive substrates with reduced defects. They
also have an increased plating speed, better coverage, wider bright range, and more tolerance to
impurities. However, they will lose their fluoride catalyst if heated over 66Â°C. Also, the fluoride catalyst
etches steel substrates, resulting in iron contamination of the plating solution. An increase in rectifier
voltage is required if metallic impurities (Ni, Fe, Cu and Cr 3 ) are permitted to build over 7.5 g/liter.
Because of the second catalyst and the need for additional analysis, these processes are more expensive and
costly to operate than single-catalyst processes.
Tri-catalyzed Hexavalent Processes. These processes are similar to co-catalyzed processes except for the
addition of a proprietary organic catalyst. This improves the cathode deposition efficiency and chromium
coverage in the low-current-density areas. This process is the most expensive decorative hexavalent process
to operate but the improved low current density coverage justifies the cost in some operations.
Trivalent Chromium Processes. Platers switch to these processes primarily for increased productivity and
improved
environmental/health/safety factors. The improved coverage and throwing powers (similar to nickel), faster
plating speed,
the lack of burning and white wash, and a complete tolerance to current interruption all lead to reduced
rejects and, in many cases, more parts on the plating rack. These factors along with a simplified method to
maintain the purity of the solution and to waste treat it, if necessary, most times makes it less expensive
per part to plate even though the operating solution is more expensive to purchase. These processes are
similar to nickel processes in that they have to be analyzed and maintained more frequently than hexavalent
chromium processes. The slight difference in deposit appearance and the need to passivate some thin nickel
(under seven microns) parts are cited by some as reasons not to convert to trivalent chromium processes.
Specialty Processes. Dark gray to black deposits are available from both hexavalent and trivalent chromium
processes. The hexavalent processes are used for solar collectors and both are used for decorative
applications. Other than the additives used to darken the deposits, these processes operate similarly to
others in the same family of processes. Hexavalent â€œcold chromiumâ€ (16â€“21Â°C) processes are used
where plating efficiency is less important than coverage in the very low-current-density areas. They are
more difficult to operate and use different sulfate (450â€“550:1 for CrO 3 :SO4 ) and fluoride concentrations
than typical hexavalent chromium processes. Barrel chromium processes are also available by using special
hexavalent formulations in specially designed barrels.
Hard Chromium Plating
Hard (functional) chromium coatings are typically thicker than 1.2 Î¼m and in some applications can be
more than 100 Î¼m thick. Chromium deposits impart functional qualities of wear and corrosion resistance,
lubricity and release properties to a wide range of substrates. Substrates that are chromium plated include
hardened and unhardened steels, tool steels, stainless steels, cast iron and aluminum. Chromium coatings
allow the use of lower-cost or lighter substrates, also the unique engineering properties of electrodeposited
chromium that cannot be attained by substrates. Chromium coatings are very cost-effective compared to
many coating processes.
Chromium coatings resist corrosion in various environments. 3 They are especially resistant to corrosion in
oxidizing environments. Chromium coatings are used in the automotive, agricultural, chemical, petroleum,
and manufacturing industries. For more severe applications duplex coatings are used. First a layer of nickel
or electroless nickel is applied, then chromium is plated. Some duplex coatings consist of a chromium layer
that is plated and ground and then another chromium layer.
Hard Chrome Chemistries
There are three predominant hard chromium plating processes: conventional, fluoride (mixedcatalyst), and
etch-free high-efficiency. All of the baths contain chromium (VI) oxide commonly referred to as chromic
acid (CrO3 ) and sulfate. The sulfate and fluoride compounds act as catalysts. The etch-free high-efficiency
bath contains a non-halide catalyst. Chromium cannot be electrodeposited from an aqueous CrO 3 solution
unlessone or more catalysts are present. Depending on which catalysts are present and the plating
parameters, between 10 and 30% of the cathodic current will be used to reduce hexavalent chromium (Cr 6+ )
to chromium metal. Their deposit properties and operating conditions are summarized in Table IV. The
etch-free high-efficiency process will be referred to as the etch-free process.
Figure 1. Photomicrographs of anodically etched chromium deposits from high-efficiency etch-free, fluoride,
and conventional baths. The samples were plated under typical conditions for each bath. The cross sections
were polished prior to etching.
Corrosion resistance of a chromium plated part is influenced by the substrate quality, pretreatment,
plating and posttreatment. The optimum plating process should produce the least amount of nodules and
the most microcracks for the best corrosion resistance. The microcracks of etched samples are shown in
Figure 1. These figures show that as the microcrack density increases the depth of the etched cracks
decreases. Corrosion resistance of identical samples plated under optimum conditions for each of the three
baths is shown in Figure 2. The improved corrosion resistance of the etch-free process is due to a higher
microcrack density and less nodular deposit.4
Figure 2. The chromium deposit thicknesses were 25 Âµm (1 mil) and the corrosion testing was conducted
according to ASTM B117. Samples were electroplated from etch-free, fluoride, and conventional baths, under
optimum conditions for each chemistry. The samples were tested as plated without any post finishing.
Wear resistance is related to the deposits' hardness and toughness. Abrasion and sliding wear resistance
data is shown in Figures 3 and 4. The etch-free process contains the smallest grains or crystallites of the
three types of deposits and wears the least of the three processes. 5 Wear is also related to the microcrack
density and oxygen content of the deposit.
The operating window is defined by the ranges of temperature, current density, and composition in which
acceptable deposits are plated. Conventional chemistry has the smallest operating window, the fluoride
process has an intermediate operating window and the etch-free process has the largest operating window.
The fluoride process has limited practical temperature range due to the volatility of the fluoride at higher
temperatures. Figure 5 depicts the variation of efficiency and microcrack density as a function of ratio
(sulfate concentration varied), compared to values obtained at a 100:1 ratio, for conventional and the etch-
free processes. The conventional process has higher variations since it is a single-catalyst system.
Deposition rate is a function of cathodic efficiency and the current density. Figure 6 shows the deposition
rates for the three processes. At the same current densities the etch-free process is up to 60% faster than
conventional, and up to 20% faster than the fluoride process. Due to catalyst stability, the etch-free process
can be operated at higher current densities and temperatures than the fluoride process.
Figure 3. Taber, dry abrasive wear with 1kg load on CS-10 wheels after 10,000 cycles. The results are the
average of three tests.
Energy Cost. At an electricity cost of $0.8/kWh the power cost is about $6/kg of CrO3 for an etch-free
deposit. The power cost of a conventional deposit would be $11/kg and for the fl uoride process would be
$8/kg. The etch-free process has lower power costs due its higher effi ciency and lower voltage (compared
to the fluoride process). The fluoride process will have a higher average voltage due to the substrate
etching. The conventional and fluoride have 80% and 30% higher power cost respectively, compared to the
etch-free process.
Anode Cost. Anodes last about three times longer in a conventional or etch-free process than anodes in the
fluoride bath. A large tank using the fluoride process can have an annual anode cost of $60,000. The savings
with a conventional or etch-free process would be about $40,000/year. Additional savings can occur by
switching from the more expensive lead-tin alloy required in fluoride processes to the less expensive lead-
antimony anodes.
Low-Current-Density (LCD) Etching. LCD etching occurs at lower cathodic current densities than where
plating occurs. Etching is minimal unless fluorides or chlorides are present. These halides attack the oxide
that protects metals and allow the hydrogen to etch the substrate. The LCD etch rates of iron samples are
shown in Figure 7 for the three chemistries. The etch-free and conventional chemistries etch 1,000 times
less than the fluoride process.
Figure 4. Lubricated sliding wear with 340 kg load for five hours. The results are the average of three
chromium plated test pins against 1137 vees.
Difficult to Plate Substrates. Nickel, high-nickel alloys and tool steels can most easily be plated in the
fluoride process. Fluoride provides very good activation for many substrates with an immersion or anodic
etch. With the use of an activating solution, anodic etch and or a hydrogen wash; nickel, high nickel alloys,
and tool steels can be plated in conventional and etch-free processes with the same adhesion strength as
with a fluoride process. When the fluoride process is used the LCD areas must be masked to prevent etching
of the substrate.
Additional Processes
Higher-Speed Etch-Free Processes. The etch-free catalyst is stable and non-volatile at higher
temperatures, allows the use of this type of chemistry at higher current densities. Current densities of up to
200 A/dm2 can be used to obtain efficiencies of 30% and deposition rates of 4.6 Î¼/min. These deposition
rates are about 10 times faster than plating speeds obtained from conventional chemistries. Higher plating
speeds allow smaller or fewer plating tanks and allows inline plating with other production processes.
Figure 5. Variation of efficiency and microcrack density as a function of ratio (sulfate) for conventional and
the etch-free processes.
Self-Regulated Processes. Numerous self-regulated conventional and high-speed fluoride processes are
available. These chemistries contain sparingly soluble compounds to control the sulfate concentration and or
the fluoride concentrations. The chemistries are partially or completely self-regulated and in some cases
platers need only to maintain the chromic acid
concentration to maintain the plating process.
Crack-Free Processes. Original deposits from crack-free processes contain no microcracks. These coatings
have niche uses. Time, mechanical, or thermal stresses can cause these coatings to form macrocracks.
Crack-free deposits are softer than microcracked deposits.
Figure 6. Deposition rate for etch-free, fluoride, and conventional baths. Fluoride data was from a
customer sample plated in the laboratory.
Equipment
Anodes. Insoluble anodes are used for hexavalent chromium plating. Lead alloys with 7% tin or 6% antimony
or tin and antimony are the most common anodes used. Lead/tin alloy anodes are more corrosion-resistant
and last longer than lead-antimony alloy anodes. Lead-tin alloy anodes should be used in fluoride baths.
Lead-antimony alloy anodes are more rigid than the lead-tin alloy and must be used in deep tanks. Lead-tin-
antimony alloys give some of the advantages of both alloying metals.
Different types of insoluble anodes are used for trivalent chromium plating depending upon the formulation.
One process uses special graphite anodes that will last â€œindefi nitelyâ€ if not mechanically damaged.
Another process uses titanium anodes coated with metal oxide that needs to be recoated every several
years. Both anodes eliminate the creation of hazardous
lead salts in the plating solution.
Rectifiers. Direct-current rectifiers should typically have a voltage range of between 9 and 15 V and
sufficient amperage for the tanks. In hexavalent chromium plating it is critical that ripple (alternating
current), over the full range of amperage that will be used, is less than 5%. High ripple can cause soft and
dull chromium and poor adhesion.
Trivalent chromium processes do not require low-ripple rectifiers. Nickel plating rectifiers with a voltage
range of 6â€“12
V can be used. Fifteen-volt rectifiers are sometimes used to optimize productivity by increasing rack density
and amperage
without burning.
Figure 7. LCD (2 A/dm2) etch rates of iron for etch-free, fluoride, and conventional baths.
Tanks and Auxiliary Equipment. Hexavalent chromium tank linings may be a flexible polyvinyl chloride
material of an approved type, either sheet or sprayed. Lead-lined tanks are not recommended for fluoride
or etch-free baths. Bricks are often used to line tanks. These must be compatible with the solution. Glass-
containing bricks should not be used with
fluoride solutions.
Metallic temperature controlling coils or heat exchangers must be electrically isolated from the steam and
water lines. Titanium cannot be used with fluoride baths, while tantalum or niobium can be used. Kynar or
PTFE coils can be used in all baths. Pumps, pipes, and ventilation equipment should be made from the above
materials or from other chromic acid or fluoride/chromic acid resistant materials.
Trivalent chromium processes can use plastic, PVC, ABS, polyethylene or rubber tank liners. Copper anode
rails should be nickel-chromium plated or plastic coated to avoid possible copper contamination of the
plating solution. Under some plating conditions, heating and even cooling might be necessary. Titanium coils
with thermostat-controlled water can be used. All equipment used to store or transfer the solution must be
plastic lined to avoided metallic contamination. Ventilation is frequently not used due to a lack of misting
but plastic air ducts with airfl ow similar to what is employed on nickel electroplating tanks may be used.
Purification. Some trivalent chromium processes use ion exchange resins to remove nickel, copper, iron,
and zinc contamination from the plating solution. The operating solution may be passed directly through the
resin even while plating. The regeneration solutions for the resin goes directly to a normal nickel and
chromium waste treatment system along with the rinse water containing trivalent chromium solution.
Plastic lined fi lter pumps containing carbon can be used to remove organic contamination if necessary.
Continuous solution filtration is not required. Since contaminants can be easily removed, atmospheric
evaporators are frequently used to evaporate water from the plating solution so that dragged out plating
solution can be returned to the plating tank.
Filtration is used in plating solutions that are used for plating chromium on optically flat rolls. Filtration is
occasionally used
in other applications. The proper filters must be used and must be precleaned and replaced on a regular
schedule. If
they break down they can cause pitting in the chromium.
Decorative hexavalent chromium solutions are very seldom filtered because particulate matter in the
solution typically
does not cause a plating problem. PFD
METHANE SULFONIC ACID
PRODUCT IDENTIFICATION
CAS NO.
75-75-2

METHANE SULFONIC ACID

EINECS NO. 200-898-6
FORMULA
CH3SO3H
MOL WT.
96.10
HS CODE

2904109000
TOXICITY
Oral rat LD50: 200 mg/kg
SYNONYMS MSA, Sulphomethane; Acide methanesulfonique;
Acide methanesulfonique, Kyselina methansulfonova; Methylsulphonic acid; ácido metanosulfónico;
Methansulfonsäure;
DERIVATION Mercaptomethane, Methanesulfonyl chloride (MSC)
CLASSIFICATION

Sulfonated hydrocarbon derivative
PHYSICAL AND CHEMICAL PROPERTIES

PHYSICAL STATE
Clear, Colorless liquid.

MELTING POINT 18 - 20 C
BOILING POINT 167 C
SPECIFIC GRAVITY 1.345
SOLUBILITY
Soluble in water. Slightly in toluene. Insoluble in paraffins.

pH
VAPOR DENSITY
AUTOIGNITION

NFPA RATINGS
Health: 3; Flammability: 1; Reactivity: 2; Special Hazard: W
REFRACTIVE INDEX

FLASH POINT > 109 C
STABILITY Stable under ordinary conditions
APPLICATIONS
Sulfonic acid is a compound with general formula RSO2OH, where R is an aliphatic or aromatic hydrocarbon.
It is a derivative of sulfuric acid (HOSO2OH) where an OH has been replaced by a carbon group or a
compound where a hydrogen atom has been replaced by treatment with sulfuric acid; for example, benzene
is converted to benzenesulfonic acid (water-soluble). Sulfonic acid has a sulfur atom bonded to a carbon
atom of a hydrocarbon and bonded also to three oxygen atoms, one of which has been attached to a
hydrogen atom. Sulfonic acid is acidic due to the hydrogen atom, stronger than a carboxylic acid. Sulfonic
acid is one of the most important organo sulfur compounds in organic synthesis. Sulfonic acids are used as
catalysts in esterification, alkylation and condensation reactions. Sulfonates are salts or esters of sulfonic
acid. Sulfonic salts are soluble in water. Sulfonic acid and its salts present in organic dyes provide useful
function of water solubility and or improve the washfastness of dyes due to their capabiltity of binding more
tightly to the fabric. They are widely used in the detergent industry. Alkylbenzene sulfonic acid is the
largest-volume synthetic surfactant because of its relatively low cost, good performance, the fact that it
can be dried to a stable powder and the biodegradable environmental friendliness. Sulfonate cleaners do
not form an insoluble precipitates in hard water. Sulfonic acid salts and esters are intermediates widely
used in organic synthesis and particularly phenolic compounds and cation exchange resins. They are
synthetic intermediate for a number of biologically active compounds and pharmaceutical candidates such
as sulfa drugs. Short carbon chain metallic sulfonate is used in electroplating which is a process for applying
a metallic coating on a metal surface by electrodeposition from a suitable electrolyte solution for imparting
corrosion resistance and direct production of printed circuit boards without etching out of a piece of copper
sheet. Methanesulfonic acid is used as the acid electrolyte in the electroplating because many metals which
are not soluble in mineral or organic acids are soluble, particularly tin and lead plating. Stannic sludge
formation is rare as methanesulfonic acid is a non-oxidizing acid. Electroplating baths for lead frames,
connectors, printed circuit boards, and wire are complex of methanesulfonic acid itself and its salts along
with additives enhancing the performance.
Methylsulphonic acid has applications in the fields include:
* Electroplating and electrochemical processes

* Alkylation, esterification and condensation reactions
* Lead recovery
* Chemical intermediate for manufacture of drugs and pesticides
* Petroleum refining and lube oil additives
* Extraction and process solvent
* Plastic stabilizers
Mesyl Chloride is widely used as a catalyst, chlorination agent and stabilizer for organic synthesis and as an
intermediate for photographic chemicals, agrochemcials, dyses and pharmaceuticals. It can be used as a
bactericide.
Anhydride is a chemical compound formed by the abstraction of a molecule of water, H2O, from a
substance. The term acid anhydride is restricted sometime to the anhydride formed especially from an acid
by dehydration or one that revert to the original substance upon hydration. In case of bimolecular, it can be
composed of two molecules of the corresponding acid. The term mixed anhydride is an acid anhydride
composed of two different acids. Examples are adenosine triphosphate or an aminoacyl adenylate. The
anhydrides of bases are oxides. Anhydrides of inorganic acids are usually oxides of nonmetallic elements.
Carbon dioxide (CO2) is the anhydride of carbonic acid, dinitrogen pentoxide (N2O5) is the anhydride of
nitric acid, and, phosphorus pentoxide (P2O5) is the anhydride of phosphoric acid, and sulfur trioxide (SO3)
is the anhydride of sulfuric acid. Examples of inorganic anhydrides include dinitrogen pentoxide, which is
the anhydride of nitric acid, and sulfur trioxide, which is the anhydride of sulfuric acid. Organic anhydrides
contain the carbonyl group (CO). Organic anhydrides are formed by the condensation of original acids.
Lactone, an internal cyclic monoester, is an anhydride derived from the hydroxyl and carboxyl radicals. The
names of anhydrides derived from carboxylic acids are given first from the original acid followed by the
separate word anhydride. Anhydrides are more reactive than the parent acids. Anhydrides are typically not
target molecules, but rather they are used as intermediates for the synthesis of other organic members such
as esters and amides for the industrial applications include dyes, pharmaceuticals, pesticides, plastics,
fibers, curing agents, plasticizers and many others. Methanesulfonic anhydride is useful in the reaction for
aromatic alkylation.
SALES SPECIFICATION

70% GRADE

85% GRADE

99% GRADE
APPEARANCE

Colorless to pale yellow liquid

PURITY
70% min

85% min

99.0% min
OXIDIZABLE MATTER

20ppm max

20ppm max

20ppm max
Cl ION

10ppm max

20ppm max

100ppm max
Fe ION

10ppm max

10 ppm max

10ppm max
SULFATE ION

200ppm max

200ppm max

200ppm max
HEAVY METALS

10ppm max

10ppm max

10ppm max
COLOR (APHA)

25 max

25 max

50 max
TRANSPORTATION
PACKING 250kgs in Drum , Iso-Tank
HAZARD CLASS
8 (Corrosive Material) 6.1

UN NO. 2586 (70%) 2922(85%)
OTHER INFORMATION
Hazard Symbols: C, Risk Phrases: 34, Safety Phrases: 26-36-45
PRICE
US$8.500/mt
1. A piston ring having improved abrasion and scuff resistance comprising:
a metal piston ring body, and
a layer on said body which is the solidified deposit resulting from the simultaneous application onto a wear
surface of said piston ring body of molten molybdenum and molten iron alloy wherein said molybdenum and
said iron alloy are applied in approximately equal amounts,
said iron alloy being selected so that the said layer exhibits a hardness value of at least about HRC 25,
said layer consisting of a mixture of particles of said iron alloy, an alloy of said iron alloy and molybdenum,
and molybdenum, surface portions of said layer being oxidized to iron oxide and molybdenum oxide, and
said layer further containing voids.
2. The piston ring of claim 1, wherein said iron alloy is a carbon steel containing about 0.8% carbon.
3. The piston ring of claim 1, wherein said iron alloy is a 13 chrome stainless steel.
4. A piston ring having improved abrasion and scuff resistance comprising:
a metal piston ring body, and
a layer on said body which is the solidified deposit resulting from the simultaneous application onto a wear
surface of said piston ring body of molten molybdenum and molten iron alloy wherein said molten
molybdenum is present in an amount of about 80% and said iron alloy in an amount of about 20%,
said iron alloy being selected so that the layer exhibits a hardness value of at least about HRC 25,
said layer consisting of a mixture of particles of said iron alloy, an alloy of said iron alloy and molybdenum,
and molybdenum, surface portions of said layer being oxidized to iron oxide and molybdenum oxide and said
layer further containing voids.
5. The piston ring of claim 4, wherein said iron alloy is a carbon steel containing about 0.8% carbon.
6. The piston ring of claim 4, wherein said iron alloy is a 13 chrome stainless steel.
Description:
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to piston rings which are for use in internal combustion engines and which have good
resistance to friction and wear. Recently, the compression ratio and the revolution speed of internal
combustion engines have been considerably increased in order to provide more efficient engine
performance. Accordingly, the piston rings used in internal combustion engines are required to have greater
wear resistance, so as to withstand the severe conditions of the environment in which they must operate
effectively. The degree of wear resistance of piston rings depends upon a number of factors including their
ability to resist abrasion, i.e., the grinding abrasive action imparted by solid particles of high hardness, and
their ability to resist scuffing. Therefore, in order to enhance the effective wear resistance of piston rings
for use in modern internal combustion engines, it as been desirable to improve both the abrasion resistance
and the scuffing resistance of such piston rings.
Discussion of Prior Art
Heretofore, various piston rings have been known which provide enhanced wear resistance. Such piston rings
include those which are chrome plated on their sliding surfaces (hereafter referred to as chrome plated
piston rings). Piston rings having a coating of molybdenum deposited on their sliding surfaces have also been
known (hereafter referred to as molybdenum deposited piston rings).
The chrome plated piston rings have proved to be unsatisfactory, however, due to the fact that chrome
plating is an expensive operation and also due to the fact that the resulting piston rings do not exhibit a
sufficiently high degree of scuff resistance. Similarly, the molybdenum deposited piston rings also have
failed to attain extensive commercial usage because of high cost and poor abrasion resistance.
Consequently, neither the chrome plated piston rings or the molybdenum deposited piston rings have been
widely accepted because they are incapable of providing a sufficiently high degree of resistance to both
abrasion and scuffing, which are necessary properties if the piston rings are to have good wear resistance.
Summary of the Invention
The present invention overcomes the above-mentioned problems of the prior art by providing piston rings
having satisfactory resistance to both abrasion and scuffing action. Briefly stated, there is provided in
accordance with this invention a piston ring provided on its outer peripheral surface with a deposit of a
composite alloy which imparts excellent wear resistance to the piston ring. The deposited composite alloy
which is coated on the outer peripheral surface of the piston ring is formed by the simultaneous spraying of
from about 30 to 95% of molten molybdenum and from about 5 to 70% of a molten iron alloy. The resulting
coating comprises iron alloy, molybdenum, combinations of iron alloy and molybdenum and voids.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are cross-sectional views of piston rings having spray deposited layers in accordance with this
invention.
FIG. 3 is an enlarged fragmentary cross-sectional view of a portion of a piston ring provided with a spray
deposited coating in accordance with the invention.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with this invention piston rings of improved wear resistance are produced by depositing on
the outer peripheral surface of a piston ring a coating formed by the simultaneous spraying of from 30 to
95% of molten polybdenum and from 5 to 70% of molten iron alloy to produce a surface resistant to both
abrasion and scuffing, the surface comprising iron alloy, molybdenum, combinations of the iron alloy and
molybdenum and voids.
If less than about 30% of molybdenum is employed, the piston ring does not have the requisite hardness. On
the other hand, if more than 95% of molybdenum is deposited a substantial reduction in overall physical
strength of the deposited layer is experienced, with consequent impairment of abrasion resistance.
If less than 5% of the iron alloy is deposited, the physical strength of the deposited layer is reduced, as is
the abrasion resistance. A deposit containing more than 70% of the iron alloy does not provide the
correlated effect of a proper mixing of iron and molybdenum which results in inherently improved abrasion
and scuff resistance in the piston rings.
In accordance with the invention, one of the most advantageous features of the piston ring is the firm
bonding between the metallic particles in the deposited coating and the underlying piston ring structure, so
that separation of high hardness solid particles from the deposited coating by frictional and sliding contact
with the mating member during operation of the piston ring is minimized. Consequently abrasion of the
mating member caused by the separated particles is also minimized and a piston ring of greatly improved
abrasion resistance is obtained.
By contrast, piston rings of the prior art which include a deposited molybdenum layer normally exhibit
extremely low tensile strength, on the order of 450 kg/cm 2 , which is believed to represent poor or loose
bonding between these solid metal particles in the deposited layer, thus leading to poor abrasion resistance.
In the present invention, the presence of particles of the high temperature iron alloy in the molten metal
which forms the deposition layer also facilitates firm bonding of the layer to the underlying piston ring
structure and improves alloying of the molybdenum particles and iron alloy particles during formation of the
deposition coating. This results in a rigidly bonded unitary structure including the difficulty bonded
molybdenum particles securely supported and bound by the alloy combination of iron alloy and
molybdenum. See FIG. 3 of the drawing wherein the molybdenum particles are represented by numeral 1
and the alloy combination of iron alloy and molybdenum is represented by numeral 2.
In the structure illustrated in FIG. 3, the iron alloy particles are designated by reference numeral 3, the
voids by reference numeral 4 and the matrix by reference A.
The entire deposited coating thus provides an improved and more rigid bonding strength (tensile strength)
and better abrasion resistance, than the prior art piston rings.
The deposition coating of the present invention also provides a superior lubrication characteristic due to the
voids (FIG. 3, reference 4) which serve to retain a lubricant between the material particles in the deposition
layer. This function is also found in the prior art piston rings having a molybdenum deposition layer. In
addition to the above, the composite alloy deposition coating on the piston ring of the present invention
consists of the iron alloy, the combination of iron alloy and molybdenum, the molybdenum particles and the
voids and includes shallow recesses which are formed on the iron alloy particles due to the difference in
hardness of the iron alloy particles and the molybdenum particles and the consequent different wearing
effect imposed on the iron alloy particles and the molybdenum particles.
The scuffing resistance of the piston rings of the present invention is further enhanced by the presence of an
antifriction iron oxide film formed on a portion of the surface of the iron alloy particles during the
formation of the deposition coating. The iron oxide film has an extremely low coefficient of friction which
results in improved scuff resistance. Similarly, molybdenum oxide is formed on the molybdenum particles
which provides an additional benefit in terms of scuff resistance.
From the foregoing, it should be readily apparent that an improved piston ring has been described which
includes a deposited composite alloy coating formed by spraying a molten material containing from 30 to
95% molybdenum and from 5 to 70% iron alloy so as to cover the sliding surfaces of a piston ring. The thus
formed deposited composite alloy coating consists of iron alloy particles, particles of a combination of iron
alloy and molybdenum, molybdenum particles and voids and provides improved resistance to abrasion and
scuffing due to the inherent properties and characteristics of the individual particle components and by the
correlation of the particles of the various materials in the deposition coating.
In forming the piston ring of the present invention various carbon steels may be used, such as 13 chrome
stainless steel. It is believed to be essential, however, that the iron alloy which is selected should be one
such that the entire deposited coating exhibits a hardness above HRC 25. Iron alloys giving a hardness value
in the deposited layer lower than HRC 25 should be avoided.
The production of piston rings in accordance with the present invention is set forth in the following
examples.
EXAMPLES 1-9
Coatings of molten metal deposition layers were applied to normal cast iron test pieces for piston rings on
the outer peripheral surfaces. The coatings were 0.3 mm thick and the test pieces had the following
compositions:
Test Piece Composition
______________________________________
% Total carbon 3.5 Silicon 2.6 Manganese 0.6 Iron Balance
______________________________________
These layers were formed by simultaneously spraying molten molybdenum and molten iron alloy under the
following conditions:
Spraying gun; Meteco 3K Type spraying gun
O 2 gas pressure; 30 lb/in 2

O 2 gas flow rate; 2.57 m 3 /hr
C 2 h 2 gas pressure; 15 lb/in 2
C 2 h 2 gas flow rate; 1.57 m 3 /hr
Air pressure; 45 lb/in 2
Air flow rate; 32.6 m 3 /hr
The iron alloys applied in each respective example had the following compositions:
________________________________________________________ __________________
Component C Si Mn Ni MO Cr Fe
________________________________________________________ __________________
No. 1 & 5
0.7 0.2 0.7 2.0 0.3 1.0 Balance
No. 2 & 7
0.8 0.2 0.7 -- 0.3 1.2 Balance
No. 3 0.8 0.2 0.7 -- -- -- Balance
No. 4 0.8 0.2 0.7 -- -- 1.2 Balance
No. 6 0.3 0.2 0.6 -- -- 1.3 Balance
No. 8 0.3 0.2 0.8 -- -- -- Balance
________________________________________________________ __________________
After application of the deposition layers, the test pieces were tested on a rotary disc tester composed of
an alloy of 2.9% total carbon, 2.2% silicon; 0.6% manganese and 94.3% of gray cast iron under the following
conditions:
Rotary tester speed -- 5 m/sec.
Friction load -- 25 Kg/cm 2
Lubricant temperature -- 80° C
Amount of lubricant -- 0.6 1/hour

______________________________________
Lubricant- Daphne oil No. 65 50% Kerosene 50%
______________________________________
Duration of test 5 hours ##SPC1##
The following results were thus obtained in thest tests:

________________________________________________________ __________________
No. 1 2 3 4 5 6 7 8 9 (Prior Art)
________________________________________________________ __________________
Iron alloy
(%) 5 10 20 30 40 50 60 70 Molybdenum
100
Molybdenum
(%) 95 90 80 70 60 50 40 30
Rockwell
C-scale
40 40 40 40 40 40 40 37 40
Tensile
strength
1000
1300
1820
1900
2000
1950
2000
2000
450
(Kg/cm 2 )
Amount of
wearing
out (?)
3.2 2.4
0.8
0.8 1.0
1.4
2.2 4.0 4.4
________________________________________________________ __________________
Each of these deposition layers may be deposited on the outer peripheral surface of a piston ring as shown
in cross-sectional views in FIGS. 1 and 2.
While the description has been made in conjunction with a composite alloy deposition layer, it should be
noted that such composite alloy deposition coating covers all normal modifications such as might contain
additional rigid oxide, nitride, carbide, silicide, sulfide and fluoride elements.
While the invention has been particularly shown and described with reference to preferred embodiments
thereof, it will be understood by those skilled in the art that various changes in form and details may be
made therein without departing from the spirit and scope of the invention.
Arvinda Kumar
R-9/303 Sector-9
Rajnagar Ghaziabad
NCR India 201002
+919818004652
1. A heat-resistant, thermally stable, ductile piston ring for an internal combustion engine, comprising:
a generally C-shaped body comprised at least partially of fiber reinforced ceramic matrix composite
(FRCMC) material comprising a polymer-derived ceramic resin in the ceramic state of said resin and fibers,
said fibers being incorporated in the form of a fiber rope and present in an amount from 35-70 percent by
volume of said (FRCMC), said generally C-shaped body having a cross-sectional shape selected from the
group consisting of rectangular, keystone, trapezoidal, and rectangular wherein a respective corner of said
rectangle is beveled.
2. The piston ring of claim 1 wherein the polymer-derived ceramic resin is chosen from silicon-carboxyl resin
or alumina silicate resin.
3. The piston ring of claim 1 wherein the fibers comprise at least one of alumina, Nextel 312, Nextel 440,
Nextel 510, Nextel 550, silicon nitride, silicon carbide, HPZ, graphite, carbon, and peat.
4. The piston ring of claim 1, wherein the form of the fibers incorporated into the FRCMC material has a
continuous configuration, said fibers being incorporated into the FRCMC in an amount sufficient to produce a
ductility of 0.6 percent strain to failure or less.
5. The piston ring of claim 1, wherein the fibers are coated with an interface material which increases the
degree of ductility exhibited by the FRCMC material.
6. The piston ring of claim 5 wherein the interface material comprises at least one 0.1-0.5 micron thick
layer of at least one of carbon, silicon nitride, silicon carbide, silicon carboxide, or boron nitride.
7. The piston ring of claim 1, wherein the FRCMC material further comprises a filler material which
increases the hardness of the material.
8. The piston ring of claim 7, wherein the filler material comprises at least one of alumina, silicon carbide,
silicon nitride, boron nitride, tungsten carbide, titanium dioxide, chrome carbide or chrome dioxide.
9. The piston ring of claim 7, wherein the degree of hardness provided by the filler material varies with the
percentage by volume of the structure consisting of the filler material, and wherein there is a sufficient
quantity of filler material to produce a desired degree of hardness.
10. The piston ring of claim 9, wherein the percentage by volume of the FRCMC material consisting of the
filler material is about 25 percent.
11. The piston ring of claim 1, wherein the FRCMC material further comprises a filler material which lowers
the coefficient of friction of the material.
12. The piston ring of claim 11, wherein the filler material comprises at least one of carbon, silicon nitride
or boron nitride.
13. The piston ring of claim 1, wherein the percentage by volume of the FRCMC material consisting of the
filler material is about 25 percent.
14. The piston ring of claim 1 wherein said structure comprises a C-shape.
15. A method for forming a generally C-shaped heat-resistant, thermally stable, ductile piston ring,
comprising the step of:
forming a structure comprised of fiber reinforced ceramic matrix composite (FRCMC) material comprising a
polymer-derived ceramic resin in its ceramic state, formed as a fiber rope present in an amount between
35-70 percent volume of said (FRCMC) fibers, and a filler material present in an amount of no greater than
25 percent of the volume of said (FRCMC) such that at least one of (i) increased the hardness of the outer
surface of the piston ring, and (ii) decreases the coefficient of friction of the outer surface of the piston
ring, said generally C-shaped structure further being formed to have a cross-sectional shape selected from
the group consisting of rectangular, keystone, trapezoidal, and rectangular wherein a respective corner of
said rectangle is beveled.
16. A heat-resistant, thermally stable, ductile piston ring for an internal combustion engine, comprising:
a generally C-shaped body comprised at least partially of fiber-reinforced ceramic matrix composite
(FRCMC) material comprising a polymer-derived ceramic resin wherein said resin exists in its ceramic state
having a multiplicity of fibers therein, said fibers being formed as a rope and present in an amount between
35-70 percent volume of said (FRCMC) such that said generally C-shaped body has a ductility of 0.6 percent
strain to failure or less.
17. The piston ring of claim 14 wherein said generally C-shaped body is formed to have a ductility ranging
between 0.40 to 0.6 percent strain to failure.
Description:
1. Technical Field
This invention relates to a piston ring for an internal combustion engine, and more particularly, to such a
piston ring formed of a fiber reinforced ceramic matrix composite (FRCMC) material and methods for making
it.
2. Background Art
In the basic operation of a gasoline-powered internal combustion engine, a piston moving up and down
within a cylinder draws in a combustible mixture of fuel and air on its down-stroke and compresses it on its
up-stroke. The compressed mixture is then ignited and burns and expands driving the piston down. A similar
process occurs in other types of engines. Piston rings are designed primarily to seal the combustion chamber
area of the cylinder. If the piston is not properly sealed within the cylinder, blow-by occurs and the
compression of the combustible mixture is reduced or non-existent thereby reducing or eliminating the
effectiveness of that piston/cylinder within the engine. Additionally, on combustion of the mixture, piston
rings prevent blow-by of the expanding gasses between the piston and the wall of the cylinder. Piston rings
are installed near the top of the piston. The ring must exert even pressure against the cylinder wall for the
full circumference of the cylinder wall to prevent blow-by and ensure engine efficiency. Therefore, piston
rings are designed so that the diameter before installation is slightly larger than that of the cylinder bore.
As a result, piston rings are exposed to great stresses during the process of mounting them on the piston
head and tend to fracture during the installation process. The piston and piston rings are exposed to high
pressures and high pressure variations, Additionally, the piston rings are exposed to frictional heating as
well as heating due to the combustion of the fuel mixture. Hence, they are exposed to high temperatures
and temperature variations, making them prone to thermally-induced failure. While the principles of the
present invention are applicable to a wide variety of engine types, a standard cylindrical piston moving up
and down within a cylindrical cylinder of an engine block having one or more cylinders will be used as the
embodiment chosen for description hereinafter and in the drawings which accompany it. It should be
understood, however, that it is intended that the invention described and claimed herein be accorded a
breadth in keeping with the scope and spirit of the disclosure as applied to all engine types.
In a classic engine, the cylinders and pistons are made of metal. Cast iron is the conventional material used
for piston rings, though aluminum, steel and other materials are used. Conventional piston rings are often
chrome plated or molybdenum coated or coated with other materials to provide increased life and greater
freedom from scoring.
As stated previously, the standard method of sealing the space between the cylinder walls and the piston is
the piston ring. A space exists (and must exist) between the piston and the cylinder because of the
dissimilar thermal expansion of the metal components. If the piston and cylinder were sized exactly with
only enough clearance for the piston to fit within the cylinder with a coating of lubricating oil film between
them, as soon as the metal heated from the combustion within the cylinders and expanded, the piston
would seize within the cylinder. If enough clearance was provided initially to allow for expansion, the blow-
by would be so extreme that the engine would not run sufficiently to get up to temperature and create the
proper seal. Thus, the expansion space is provided and the clearance gap is closed with piston rings as
shown in FIGS. 1 and 2. There may be one piston ring, two piston rings, or more, depending on the engine
design and the objectives thereof. Regardless of the number, each piston ring 10 is disposed in a ring groove
16 in the peripheral surface of the piston 14 adjacent to the top thereof. The piston ring 10 is not a
complete circle. Rather, it is incomplete and has a gap 12 at its ends so that it can be compressed or
expanded in diameter within the ring groove 16. Typically, a piston ring 10 operates by expanding so that its
outer peripheral surface presses against the cylinder wall to seal the expansion space between the piston
14. This expansion is caused by the high pressure gases formed in the cylinder above the piston 14. These
gases flow down the between the piston and cylinder wall. These high pressure gases first force the piston
ring 10 downward in the piston ring groove 16. The gases then enter the ring groove 16 from a point above
the piston ring 10, and eventually flow behind the piston ring where they force it outwards to seal the
expansion space. The piston ring 10 is hence exposed to frictional forces due to its movement within the
ring groove 16 and up and down within the cylinder, which decrease the life of the ring due to friction-
induced wear. Hardness and lubricity of the rings are hence a desirable quality. Hardness limits the amount
of wear, such as scoring, due to friction. Lubricity between the parts is essential to provide proper
operation of the piston/cylinders and to prevent seizure of these components and also reduce friction
between the piston, piston ring and cylinder components.
Early low compression engines with piston rings made of the materials available at the time tended to form
carbon within the ring grooves over time. Recent engine designs and the materials employed for the pistons,
cylinders, and rings as well as the modern more accurately computer-controlled engines have resulted in
less tendency for there to be formation of carbon in the ring grooves which caused the piston ring to stick
within the piston groove.
While engine designs and materials have certainly improved over the years, there still remain deficiencies
such as lower than desirable fuel efficiency and higher than desirable pollution emissions. In a co-pending
application entitled HIGH-EFFICIENCY, LOW-POLLUTION ENGINE by the inventors of this application and
assigned to the common assignee, an improved fiber reinforced ceramic matrix composite (FRCMC) material
is disclosed having high breakage resistance and particular applicability to use for parts in a high
temperature internal combustion engine. This copending application was filed on Aug. 16, 1995 and assigned
Ser. No. 08/515,604. The disclosure of the co-pending application is incorporated by reference. The co-
pending application taught FRCMC pistons and cylinders. Being of the FRCMC material, the pistons and
cylinders can withstand much higher operating temperatures than conventional internal combustion engines.
Operation at higher temperatures increases fuel efficiency and reduces the pollution produced because fuel
and contaminants are more completely burned at higher temperatures. Moreover, since the coefficient of
thermal expansion of the parts is much lower, decreasing the allowance required for the dissimilar thermal
expansion of the components, much closer tolerances can be maintained without the danger of engine
seizure. Still, however, to operate at as high a compression ratio as possible without efficiency-robbing
blow-by, there must be piston rings. Conventional piston rings are not adequate, however. Despite the many
improvements in materials and wear resistance, prior art piston rings are intended for use in metal engines.
The FRCMC material of the pistons and cylinders, in conjunction with its ceramic wear coatings will quickly
erode even the hardest conventional metallic piston rings.
To prevent the common piston ring problems, car, motorcycle, truck, train, and other machinery
applications could utilize a better piston ring than is provided by current technology, especially those
employing FRCMC pistons and/or cylinders. Depending on the application, this improved piston ring should
be constructed of material that is light, long wearing, and which has a low thermal expansion so as to allow
manufacture of the engine parts to close tolerances. This ensures a longer life and improved performance
over the present technology. Additionally, this improved piston ring should be hard to endure the stresses of
piston/cylinder operation and be tolerant of high temperatures to which they will be exposed as a result of
the combustion within the cylinders and the friction of the interfacing parts. It should also be made of
material that has a low coefficient of friction so as to reduce the wear due to the friction of the various
piston components rubbing together during piston/cylinder operation.
Wherefore, it is an object of this invention to provide a lightweight, but high strength piston ring which is
ductile and fracture resistant.
It is another object of the present invention to provide a piston ring that can be used in a FRCMC cylinder or
in combination with a FRCMC piston without rapid erosion.
It is still another object of this invention to provide a piston ring that has a lower thermal expansion, so as
to allow engine parts to be machined to much closer tolerances without the danger of engine seizure.
It is still another object of this invention to provide a piston ring that exhibits high hardness and good
lubricity at elevated temperatures.
Wherefore, it is another object of the present invention to provide a piston ring which is capable of
withstanding high temperatures and thermally-induced strains.
Other objects and benefits of this invention will become apparent from the description which follows
hereinafter when read in conjunction with the draw figures which accompany it.
SUMMARY
The foregoing objects have been achieved by a strong, ductile and erosion resistant/fracture-resistant
piston ring, which is light weight and capable of withstanding high temperatures and thermally-induced
strains. The piston ring is made of a fiber reinforced ceramic matrix composite (FRCMC) material. This
piston ring made of this FRCMC material also exhibits a high degree of hardness and provides good lubricity,
even at elevated temperatures, when tailored by incorporating certain filler materials. The FRCMC material
includes a polymer-derived ceramic resin in its ceramic state and fibers. The ceramic portion of the
material for the most part provides the heat-resistant capabilities of the FRCMC material, while the fibers
produce a desired degree of ductility in the FRCMC material. Ductility for the purposes of the present
invention is defined as the amount strain a sample of the FRCMC material can withstand before fracturing or
tearing. The piston ring has a C-shaped body structure.
Forming a piston ring of FRCMC material has significant advantages over the prior cast iron or steel piston
rings, or piston rings made of other materials. First, FRCMC material can be formed into practically any
shape and size desired. FRCMC material being somewhat ductile makes the piston rings fracture resistant
and capable of withstanding mechanically-induced strains associated with its expansion to install it into the
ring groove of a piston and the thermally-induced strains which may be imparted to the ring when the
internal combustion engine is operating. Additionally, the FRCMC material, especially if comprised of a
woven fiber, is very strong for a given weight. Since the FRCMC piston rings are thermally stable, that is,
have a low coefficient of thermal expansion even at high temperatures, the rings and other adjacent parts
can be manufactured to much closer tolerances without the danger of engine seizure. Additionally, the
FRCMC material has a high degree of hardness and a low coefficient of friction when appropriate filler
materials are utilized, which is maintained even at high temperatures. This reduces the wear of the piston
ring and the cylinder.
The pre-ceramic resin used to form the FRCMC material can be any commercially available polymer-derived
ceramic precursor resin, such as silicon-carboxyl resin or alumina silicate resin, and the fibers are preferably
at least one of alumina, Nextel 312, Nextel 440, Nextel 510, Nextel 550, silicon nitride, silicon carbide, HPZ,
graphite, carbon, and peat. The aforementioned degree of ductility caused by the fibers varies with the
percentage by volume of the fibers in the FRCMC material. Preferably, there is a sufficient quantity of fibers
to produce the desired degree of ductility. Specifically, the percentage by volume of the FRCMC material
consisting of the fibers is within a range of about 35 to 70 percent, which will produce a degree of ductility
between about 0.4 and 0.6 percent strain to failure. In addition, the form of the fibers incorporated into the
FRCMC material has a continuous configuration that also contributes to the degree of ductility exhibited.
The fibers are also preferably coated with an interface material that increases the ductility exhibited by the
FRCMC material so as to facilitate producing the desire degree of ductility. Specifically, the interface
material preferably includes at least one 0.1-0.5 micron thick layer of at least one of carbon, silicon nitride,
silicon carbide, silicon carboxide, or boron nitride. The FRCMC material can also further incorporate a filler
material which increases the hardness of the material. Specifically, the filler material can include one or
more of the following: carbon, alumina, silicon carbide, silicon nitride, boron nitride, tungsten carbide,
titanium dioxide, chrome carbide and chrome dioxide. The degree of hardness provided by the filler
material varies with the percentage by volume of the structure consisting of the filler material. Accordingly,
a sufficient quantity of filler material should be incorporated to produce the desired degree of hardness. To
decrease the coefficient of friction of the piston ring, filler materials such silicon nitride and/or boron
nitride can be incorporated. Thus, the addition of silicon nitride and/or boron nitride can both increase
hardness and decrease the coefficient of friction.
The piston ring of the present invention is preferably formed by employing continuous woven fiber rope to
achieve a high degree of ductility for a given weight. The preferred embodiment includes a ceramic C-
shaped body comprised of FRCMC material having a fiber rope which produces radial ductility when this
fiber rope is placed circumferentially around the piston ring. The fiber orientation is in the direction of the
loading. This preferred embodiment is preferably made using a resin transfer molding (RTM) process in
conjunction with a fiber rope preform to enhance ductility and ceramic, metallic or organic fillers to
enhance hardness and lower the coefficient of friction.
In addition to the just described benefits, other objectives and advantages of the present invention will
become apparent from the detailed description which follows hereinafter when taken in conjunction with
the drawing figures which accompany it.
DESCRIPTION OF THE DRAWINGS

The specific features, aspects, and advantages of the present invention will become better understood with
regard to the following description, appended claims, and accompanying drawings where:
FIG. 1 is a simplified side view of a prior art metal piston ring.
FIG. 2 is a cutaway view though one side of the piston ring of FIG. 1.
FIG. 3 is a simplified side view of a piston ring according to the present invention.
FIG. 4 is a cutaway view through one side of the piston ring of FIG. 3.
FIG. 5 is a cutaway view of a piston ring having a cross-section with a tapered wall.
FIG.6 is a cutaway view of a piston ring having a cross-section which includes a beveled corner.
FIG. 7 is a cutaway view of a piston ring having a keystone shaped cros-section.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following description of the preferred embodiments of the present invention, reference is made to
the accompanying drawings which form a part hereof, and in which is shown by way of illustration specific
embodiments in which the invention may be practiced. It is understood that other embodiments may be
utilized and structural changes may be made without departing from the scope of the present invention.
The structure of the piston ring; the materials of which the piston ring may be made; tailoring specifics and
methods of making the preferred embodiment of the piston ring will be discussed in turn in the following
paragraphs.
Structure
FIG. 3 depicts an embodiment of a piston ring 20 in accordance with the present invention. In this
embodiment, the piston ring of the invention consists of a C-shaped body fabricated of FRCMC material. The
piston ring 20 has generally circular body shape. However, the piston ring 20 has a gap 22 in the body. FIG. 4
shows a section along line 4--4 of FIG. 3. The piston ring 20 is disposed within a groove 26 in the piston head
14. One of more rings 20 may be employed within a given piston head.
It should be noted that the piston ring can have various cross-sectional shapes as shown, for example, in
FIGS. 5, 6 and 7. FIG. 4 shows a piston ring 30 cross-section that has a tapered wall 32. This type of ring wall
32 is often tapered approximately one degree. This provides initially a line contact with the cylinder wall
(not shown), which because of high unit pressure quickly seats, assuring improved sealing against
compression losses. FIG. 5 shows a piston ring 40 which has a cross-section with a beveled inside upper
corner 42. This form of piston ring cross-section utilizes gas pressure to cause the bottom edge of the ring to
contact the cylinder wall (not shown) with high pressures. This helps to seal against compression losses. FIG.
6 shows a piston ring 50 which has a key-stone cross-sectional area. Several advantages exist to this
keystone form of the piston ring. Because of its wedge or keystone shape, the forces of compression cause a
certain degree of motion between the ring and the piston. The action is claimed to free the ring of carbon
accumulation, thereby preventing sticking of the ring in the groove. However, the recitation of these
specific shapes of piston rings is not meant to limit the present invention. In general, any type of piston ring
can be formed of the FRCMC material because it lends itself to be easily formable into even the most
complex shapes.
Materials
Materials appropriate for use in forming FRCMC piston rings generally are made by combining any
commercially available polymer-derived ceramic precursor resin, such as silicon-carboxyl resin or alumina
silicate resin, with some type of fibers. Examples of appropriate ceramic precursor resins include
BLACKGLAS™ sold by Allied Signal, CERASET™ sold by the Lanxide Corporation, SYLRAMIC™ sold by Dow
Chemical, STARFIRE™ sold by the Starfire Corporation, and TONEN™ sold by the Tonen Corporation. An
example of an appropriate alumina silicate pre-ceramic resin is CO-2 sold by Applied Polymerics. Examples
of types of fibers which might be employed in an FRCMC material include alumina, Nextel 312, Nextel 440,
Nextel 510, Nextel 550, silicon nitride, silicon carbide, HPZ, graphite, carbon, and peat. To add toughness
to the material, the fibers being incorporated into the FRCMC layers are preferably first coated with an
interface material such as carbon, silicon nitride, silicon carbide, silicon carboxide, boron nitride or multiple
layers of one or more of these interfacial materials. The interface material prevents the resin from adhering
directly to the fibers of the fiber system. Thus, after the resin has been converted to a ceramic, there is a
weak interface between the ceramic matrix and the fibers. This weak bond enhances the ductility exhibited
by the FRCMC material. In addition, the FRCMC material can include filler materials preferably in the form
of powders having particle sizes somewhere between about 1 and 60 microns. These filler materials are used
to increase the hardness and the lubricity of the FRCMC material as appropriate for a piston ring. The resin,
fiber, and possibly filler material mixture is generally formed into the shape of the desired structure via one
of a variety of methods and heated for a time to a temperature, as specified by the material suppliers
(typically between 1,500° F. and 2,000° F.), which causes the resin to be converted into a ceramic.
Tailoring for Specific Properties
The fibers and interface materials incorporated into the FRCMC material provide the ductility and so impart
strength to the material. Ductility is the measure of how much strain the structure can withstand before
fracturing or tearing. This ductility gives the FRCMC material the strength to withstand the rigors of ring
installation, frictional forces, high pressures and thermally-induced strains associated with a widely varying
temperature environment. The tailoring process is a subject of a co-pending application entitled POLYMER-
DERIVED FIBER REINFORCED CERAMIC MATRIX COMPOSITE MATERIALS HAVING TAILORED DUCTILITY,
HARDNESS AND COEFFICIENT OF FRICTION CHARACTERISTICS, having the same inventors as the present
application and assigned to a common assignee. This co-pending application was filed on Oct. 14, 1998 and
assigned Ser. No. 09/172,361. The disclosures of the co-pending application are incorporated by reference.
Generally, a piston ring made of FRCMC material will be thermally stable; that is, it will have a low
coefficient of expansion even at high temperatures. Other characteristics of the FRCMC material can also be
of interest in the design of the piston ring according to the present invention, such as the hardness and
coefficient of friction of the material. The harness and coefficient of friction of the FRCMC material can
controlled to some extent by the addition of certain filler material to the composite.
The above-described tailoring involves incorporating the appropriate type of fibers into the composite in
sufficient quantities to produce a desired degree of ductility. Additionally, the tailoring can involve
incorporating the filler material into the composite in sufficient quantities to produce a desired degree of
hardness and/or coefficient of friction. In both cases, the degree to which these respective characteristics
are exhibited varies with the type and percent by volume of fibers and filler materials incorporated into the
structure.
The ductility exhibited by a FRCMC material can also be tailored by selecting the form of the fibers. Namely,
selecting a continuous or woven fiber system where the individual fibers typically run the entire length of
the FRCMC structure. This continuous fiber reinforced form would provide high strength for a given weight.
For the preferred embodiment of this invention a woven continuous fiber rope is employed to form the C-
shaped piston ring. Finally, it is noted that the choice of interface material can have an effect on the
degree of ductility exhibited by the FRCMC material. In this case it is preferred boron nitride be used as the
interface material. By way of an example, it is noted that a piston ring employing a woven continuous fiber
rope constituting about 50 percent by volume of the FRCMC structure and a boron nitride interface material
coating on the fibers, will exhibit a ductility of approximately 0.6 percent strain to failure.
Tailoring the hardness and coefficient of friction of the FRCMC material involves the addition of an
appropriate filler material, as mentioned previously. Specifically, hardness can be varied by incorporating at
least one of alumina, silicon carbide, silicon nitride, tungsten carbide, titanium dioxide, chrome carbide or
chrome dioxide as the filler material. Additionally, the coefficient of friction can be lowered by
incorporation of at least one of carbon, silicon nitride or boron nitride. However, both the hardness can be
increased and the coefficient of friction decreased by the substance(s) if silicon nitride and/or boron nitride
are employed as the filler material. In any case, it is preferred that the filler material be incorporated in
sufficient quantities to make up about 25 percent of the volume of the FRCMC material making up the piston
ring, or at least the portion of the FRCMC material disposed on the outside of the aforementioned rope.
Method of Manufacture
The piston rings of the present invention can be fabricated by using various methods. One preferred method
is resin transfer molding (RTM). The RTM process is described in a co-pending application entitled METHODS
AND APPARATUS FOR MAKING CERAMIC MATRIX COMPOSITE LINED AUTOMOBILE PARTS AND FIBER
REINFORCED CERAMIC MATRIX COMPOSITE AUTOMOBILE PARTS by the inventors herein and assigned to the
common assignee of the present application. This co-pending application was filed on Aug. 16, 1995 and
assigned Ser. No. 08/515,849. The disclosure of this co-pending application is incorporated by reference.
The RTM method described in the co-pending application generally involves forming a preform in the shape
of the part from the aforementioned fibers, which in this case constitutes a continuous, woven fiber rope;
placing the preform in a cavity of a mold having the shape of the piston rings; forcing a liquid pre-ceramic
polymer resin through the cavity to fill the cavity and saturate the preform; heating the mold at a
temperature and for a time associated with the pre-ceramic polymer resin which transforms the liquid pre-
ceramic polymer resin-saturated preform into a polymer composite part; removing the polymer composite
part from the mold; and, firing the polymer composite part in a controlled atmosphere at a temperature
and for a time associated with the pre-ceramic polymer which transforms it into a ceramic, whereby the
polymer composite part is transformed into a fiber reinforced ceramic matrix composite piston rings. If filler
materials are to be incorporated to increase hardness and/or to lower the coefficient of friction they would
be mixed with the liquid pre-ceramic resin before forcing it through the cavity of the mold. It should be
noted that the filler materials will not readily enter into the weave of the woven fiber rope structure and so
most of the filler material particles will be concentrated in that part of the FRCMC material covering the
outside of the fiber rope, where they are most needed.
The woven fiber preform in the form of a fiber rope is placed in the mold prior to assembling the mold. In
addition, the inlet to the sprue channels of the mold is connected to a reservoir containing pre-ceramic
resin. The outlet associated with the resin outlet ports of the mold is connected to a vacuum source. With
the preform in place, the vacuum source is activated for creating a vacuum and the path to the resin
reservoir is opened. Resin under pressure is forced into the mold and through the preform from the
combined pressure and the vacuum from the vacuum source until the preform is totally saturated with the
resin.
An alternate preferred method of manufacturing the piston ring in accordance with the present invention is
via a compression molding process. This process is described in a co-pending application entitled
COMPRESSION/INJECTION MOLDING OF POLYMER-DERIVED FIBER REINFORCED CERAMIC MATRIX COMPOSITE
MATERIALS having the same inventors as the present application and assigned to a common assignee. This
co-pending application was filed on Aug. 28, 1996 and assigned Ser. No. 08/704,348. The disclosure of this
co-pending application is herein incorporated by reference. The following simplified process provides an
example of using the aforementioned compression molding process to form a FRCMC piston ring:
(a) First, the fibers of the woven fiber rope as described previously are coated via well known methods with
the aforementioned interface material. In this case, one 0.1 to 0.5 micron thick layer of boron nitride was
chosen as the interface material. Once coated, the fiber rope is saturated with pre-ceramic resin, which in
the case of this example is BLACKGLAS resin. The rope is saturated with resin for two reasons. First, as the
fibers are tightly packed in the fiber rope, saturating them prior to molding ensures the resin is uniform
throughout. If the fiber rope where place in the mold dry, there is a risk that resin pushed through the fibers
during molding would not reach all areas. These dry area could undesirably weaken the structure.
(b) A second reason the fiber rope is saturated with resin is to facilitate coating the outside of the rope with
filler materials. Once the fiber rope is saturated with resin, it is coated with a filler material(s) which will
impart the desired hardness and coefficient of friction to the surface of the stem. This coating can be
accomplish via any appropriate conventional method, such as rolling the saturated fiber rope in the filler
material or tumbling the rope with the filler material.
(c) The coated resin-saturated fiber rope is then placed into the portion of a female mold die. The interior
female mold die has a shape which in combination with a male mold die forms a cavity therebetween having
the desired shape of the piston ring.
(d) Next, the male mold die is lowered and the mold compressed to form the piston ring. As the fiber rope is
compressed, excess resin is ejected from the mold through one or more resin outlet ports. The filler
material coating the exterior of the fiber rope will stay in place for the most part and mix with some of the
resin during the compression process, thereby forming an external layer which will exhibit the desired
hardness and coefficient of friction.
(e) The mold is then heated at a temperature and for a time associated with the pre-ceramic resin which
polymerizes the resin to form a fiber-reinforced polymer composite structure.
(f) Next, the polymerized composite structure is removed from the mold.
(g) And finally, the polymerized composite structure is fired at a temperature and for a time associated with
the polymerized resin which pyrolizes it to form a FRCMC structure.
Once the FRCMC piston ring is molded via the compression molding process, it is preferred that an additional
procedure be performed to eliminate pores created during the required heating cycles. Eliminating these
pores strengthens the part. Specifically, after the completion of the heating step which pyrolizes the FRCMC
piston ring, the part is immersed into a bath of a pre-ceramic resin to fill the pores. The part is then heated
at a temperature and for a time associated with the resin filling the pores so as to transform it into a
ceramic material. Unfortunately, the process of heating the resin filling the pores will create further pores.
Accordingly, it is desired that the filling and heating steps be repeated until the pore density within the
FRCMC piston ring is less than a prescribed percentage by volume. This prescribed percentage corresponds
to the point where the part will exhibit a repeatable strength from one part to the next. To facilitate the
filling step, it is preferred that the resin has a water-like viscosity. In addition, the FRCMC part could be
placed in a vacuum environment to assist in the filling of the pores.
The piston ring components can also be fabricated using other well known methods applicable to FRCMC
part formation including hot pressing, tape or tow placement, or hand lay-up. It is not intended to limit the
invention to any of the described methods. Rather any appropriate method may be employed to form the
piston rings components from the previously described FRCMC material.
Because it has qualities that conventional piston ring components do not have such as heat and fracture-
resistance under extreme temperatures, light weight, and high strength, the piston rings components made
from above-described FRCMC material have several advantages. The FRCMC piston rings are stronger than
presently used piston rings, and thereby increase the life of the ring. Additionally, the FRCMC piston rings
exhibit a lower thermal expansion and thus can be manufactured to closer tolerances. If the piston rings are
tailored using filler materials to increase hardness and lower coefficient of friction, then the piston rings
will exhibit greater hardness and lubricity over the present art.
While the invention has been described in detail by specific reference to preferred embodiments thereof, it
is understood that variations and modifications thereof may be made without departing from the true spirit
and scope of the invention. For example, while a piston ring is being described for purposes of an example
of this disclosure, the present invention would also be applicable to make the rotor seals of, for example, a
FRCMC rotary engine. Additionally, some conventional piston rings employ a groove around the exterior
circumference of the ring which is filled with various materials to increase the life of the piston ring. Such
piston ring could be similarly formed such that the FRCMC material is disposed only in the exterior,
circumferential groove. Alternately, only the ring could be made of FRCMC material and the groove could be
made of other material. Additionally, FRCMC materials could also be used to manufacture oil rings which are
designed to control the amount of oil on the cylinder walls so that there is enough for lubrication, but not
such an excess it would reach the combustion chamber. In fact, the FRCMC material could conceivably be
used to form any of the prior art piston rings, or be employed for any device that is used to seal against
compressed air losses.
Arvinda Kumar
R-9/303 Sector-9
Rajnagar Ghaziabad
NCR India 201002
+919818004652
10. A method of producing a structured hard chrome layer, comprising deposition chromium from an
electrolyte onto a workpiece, said electrolyte comprising: (a) a Cr (VI) compound in an amount
corresponding to 50 g/l to 600 g/l of chromic acid anhydride; (b) 0.5 g/l to 10 g/l of sulphuric acid; (c) 1 g/l
to 20 g/l of aliphatic sulphonic acid, that comprises 1 to 6 carbon atoms, and (d) 10 g/l to 200 g/l of at least
one compound forming a dense cathode film, said compound being selected from among ammonium
molybdate, alkali molybdate and alkaline earth molybdate, ammonium vanadate, alkali vanadate and
alkaline earth vanadate, and ammonium zirconate, alkali zirconate and alkaline earth zirconate, wherein
the cathodic current yield in the production of the structures hard chrome layer is 12% or less.
11. The method as claimed in claim 10, wherein the Cr(VI) compound is CrO3.
12. The method of claim 10, wherein the aliphatic sulphonic acid is methane
13. The method of claim 10, wherein the compound forming a dense cathode film is (NH4)6Mo7O24.4H2O.
14. The method of claim 10, wherein the electrolyte contains substantially no fluorides.
15. The method of claim 10, which comprises applying a current density of from 20 A/dm2 to 200 A/dm2 to
the workpiece.
16. A structured hard chrome layer, obtained by the method of claim 10.
17. An electrolyte, comprising: (a) a Cr (VI) compound in an amount corresponding to 50 g/l to 600 g/l of
chromic acid anhydride; (b) 0.5 g/l to 10 g/l of sulphuric acid; (c) 1 g/l to 20 g/l of aliphatic sulphonic acid,
comprising 1 to 6 carbon atoms, and (d) 10 g/l to 200 g/l of at least one compound forming a dense cathode
film, said compound being selected from among ammonium molybdate, alkali molybdate and alkaline earth
molybdate, ammonium vanadate, alkali vanadate and alkaline earth vanadate, and ammonium zirconate,
alkali zirconate and alkaline earth zirconate, for carrying out the method of claim 10.
18. The electrolyte of claim 17, wherein the Cr(VI) compound is CrO3.
19. The electrolyte of claim 17, wherein the aliphatic sulphonic acid is methane sulphonic acid.
20. The electrolyte of claim 17, wherein the compound forming a dense cathode film is
(NH4)6Mo7O24.4H2O.
21. The electrolyte of claim 18, having substantially no fluorides.
Description:
The invention relates to a method of producing a structured hard chrome layer on a workpiece, to
structured hard chrome layers obtainable thereby and to an electrolyte for carrying out said method.
Electrochemically or galvanically deposited chromium layers have been considered prior art for many years
in functional and decorative fields of use and in applications for coating electrically conductive and non-
conductive workpieces.
The use of structured, electrochemically produced hard chrome layers has gained increasing importance in
the past few years and especially recently. In particular, the use of functional structures is showing a strong
upward trend. Typical applications are found in the coating of printing rollers for better wetting thereof
with ink, in rollers for embossing metal sheets, for improving the deep-drawing processes for the automobile
industry and also in storage, for protection against wear and for reduction of friction.
However, the structured layers employed according to the prior art all have a pronounced spherical laminar
structure. The size of the spherical shapes varies between less than 1 ?m and several ?m. The degree of
occupation or the density of the spherical laminar structure is more or less variable, depending on the
particular method.
Thus, according to DE 33 077 48 A1, DE 42 11 881 A1 and DE 43 34 122 A1, structured chrome layers are
produced by variation of direct electric currents, with the build-up of the structures being influenced by
varying the height of current ramps and of current impulses.
Spherical structures are also produced according to DE 44 32 512 A1. In this case, however, their growth is
made possible by adding salts of the elements selenium or tellurium to the chrome- plating electrolyte.
According to DE 19828545 C1, the addition of 2-hydroxy-ethanesulphonate ions to the electrolyte in

combination with its temperature variation and the variation of the direct electric current applied also
results in spherical structures.
However, all of these aforementioned structured chrome layers have the same, more or less strongly
pronounced spherical characteristic, which is not suitable for all applications. Some of these layers are non-
uniform and the process for their deposition is subject to several mechanisms, which cannot be safely
controlled.
WO 02/38835 A1 discloses a method for electrolytic coating of materials, wherein a chromium alloy is
deposited from an electrolyte containing at least chromic acid, sulphuric acid, or a metal forming isopoly
anions, a short-chain aliphatic sulphuric acid, their salts and/or their halogen derivatives and fluorides. This
prior art document does not mention the production of a structured hard chrome layer.
Therefore, it is an object of the present invention to provide a method for producing a structured hard
chrome layer, which method does not have the disadvantages of the prior art.
According to the invention, this is achieved by a method for producing a structured hard chrome layer,
wherein chromium is deposited from an electrolyte on a workpiece, said electrolyte containing:
*
o (a) a Cr(VI) compound in an amount corresponding to 50 g/l to 600 g/l of chromic acid anhydride;
o (b) 0.5 g/l to 10 g/l of sulphuric acid;
o (c) 1 g/l to 20 g/l of aliphatic sulphonic acid comprising 1 to 6 carbon atoms, and
o (d) 10 g/l to 200 g/l of at least one compound forming a dense cathode film and selected from
among ammonium molybdate, alkali molybdate and alkaline earth molybdate, ammonium vanadate, alkali
vanadate and alkaline earth vanadate, ammonium zirconate, alkali zirconate and alkaline earth zirconate.
The method according to the invention is optimally suited for application in producing structured hard
chrome layers.
A structured hard chrome layer is obtained by the method according to the invention by selectively
influencing the cathode film forming during electrochemical deposition of metals, said hard chrome layer
being cup-shaped and/or labyrinth-like and/or column-shaped.
If salts are dissolved in water, they dissociate into cations and anions. At the same time, these dissociated
ions surround themselves with a hydrate sheath, i.e. water molecules deposit (as dipoles) around the cations
or the anions, respectively. During hydration, the charge number of the ions is not changed. If a hydrated
metal ion begins to migrate under the influence of electric current, it will enter near the cathode, into a
border area, between the electrolyte and the cathode.
This so-called cathode film is located directly on the surface of the workpiece to be coated, because the
workpiece is negatively switched electrically. In this phase boundary the metal ions present in the
electrolyte are first aligned by picking up electrons which are provided by the electric current from the
cathode. Located directly on the surface of the workpiece, below the diffusion zone, is an electrochemical
bilayer, also referred to as “Helmholtz bilayer”. This term relates to the electrically charged zone at the
electrolyte/electrode interface, said zone having a thickness of approximately a few atom or molecule
layers. The formation of said zone depends on ions, electrons or aligned dipole molecules. It is positively
charged on one side, negatively charged on the other side and behaves like a plate capacitor having an
extremely small plate distance. The metal atom thus formed is now present on the surface of the
workpiece. However, its condition is not yet comparable with that of an atom within the metal. The atoms
formed will only take their places in the present metal grid, if a so-called growth site is present.
The conditions of the position of the electrolytes, such as chemical composition, temperature,
hydrodynamics and electric current, are usually selected such that the basic material is uniformly covered
with the metal to be deposited. That is, the cathode film is influenced by this measure such that its
permeability for the present ions is as uniform as possible.
Chromium as an element is present in aqueous solutions, as compared with most elements that can be
electrochemically deposited, as a negatively charged complex ion, mainly as hydrogen dichromate in
strongly acidic solution.
In this complex, chromium has an oxidation state of 6. In addition, electrolytes also contain reduced
amounts of chromium (III) compounds.
If such aqueous solution is electrolysed, a solid film preventing chrome deposition forms on the cathode.
Only hydrogen is produced, which can pass through the solid cathode film due to the small radius of
hydrogen, but not the large hydrogen dichromate ions. Only by adding foreign anions, e.g. sulphate and
chloride, does the cathode film become permeable to chromium ions and deposition of chromium occurs via
various oxidation stages (see “Chemie für die Galvanotechnik” LEUTZE Verlag, second edition, 1993).
By adding to the electrolyte at least one compound forming a dense cathode film, the formation of the
cathode film is controlled such that it becomes permeable to chromium ions, so that a very dense barrier
layer forms first, which then breaks down depending on the density of the applied electric current for
coating and allows the metal structure to form with different strength or layer thickness. In this manner,
structured chromium layers are obtained, which are cup-shaped and/or labyrinth-like and/or column-
shaped.
The chrome layer obtained according to the method of the invention has high resistance to wear and
corrosion, excellent sliding properties and resistance to seizure and also an aesthetically favourable
appearance, which is achieved by hardly any other coating. Due to its cup-shaped and/or labyrinth-like
and/or column-shaped structure, the hard chrome layer can be used for many functional or even decorative
applications. Thus, for example, the specific structure of the layer ensures an improved capacity for
absorption of liquids. Further, it is possible to form a gas pad as well as to achieve an improved anchoring
ability for substances to be deposited therein, e.g. plastic materials, dyes, metals, ceramic materials,
electronic components, body-specific tissue, as a coating for implants. Further, due to its surface
topography, said specific structure enables intentional optical effects, e.g. a high adsorption capacity for
light radiation and heat radiation using solar collectors, and also decorative applications in the design field.
The term “electrolyte” in the sense of the present invention relates to aqueous solutions whose electric
conductivity results from electrolytic dissociation in ions. Accordingly, in addition to components (a) to (d)
and optionally further present additives, the electrolyte comprises water as the remainder.
The above-indicated quantities of components (a) to (d) relate to the electrolyte.
As component (a), CrO 3 is preferably used, which has proved to be particularly favourable with regard to
the electrolytic deposition of chromium.
An aliphatic sulphonic acid preferably used as component (c) is methane sulphonic acid. This acid has turned
out to be particularly favourable in forming the structured hard chrome layers having the aforementioned
properties.
As alkali ions for component (d) Li + , Na + and K + may be used. Examples of alkaline earth ions are Mg 2+
and Ca 2+ . In a preferred embodiment, component (d) is (NH 4 ) 6 Mo 7 O 24 .4H 2 O, which has turned out
to be particularly favourable in forming the structured hard chrome layer having the aforementioned
properties.
The electrolyte referred to in more detail above is substantially free from fluorides, according to a
particularly preferred embodiment. Herein, fluorides refer to both simple and complex fluorides. If fluorides
are present in the electrolyte, this will interfere with the formation of the structured hard chrome layer.
Accordingly, the term “substantially no fluorides” means that an amount of fluoride is tolerable in the
electrolyte which does not influence the formation of the structured hard chrome layer. The amount of
fluorides which are tolerable can be easily determined by the person skilled in the art. It has proven to be
favourable, if no more than 0.1 g/l is present in the electrolyte.
The electrolyte may further contain conventional catalysts assisting in chromium deposition such as SO 4 2-
and/or Cl - . These compounds may be present in the electrolyte in the usual amounts.
Using the method according to the invention, structured hard chrome layers of the type described in more
detail above are formed on workpieces. In this connection, the term “workpiece” refers to objects of any
kind which are to be provided with a structured chromium layer. These may be metal or non-metal objects.
If a structured hard chrome layer is to be formed on a non-metallic object, said object is made electrically
conductive first by applying a thin metal film.
In order to form the structured hard chrome layer on the workpiece, the latter is cathodically switched and
immersed in the electrolyte. A direct current, for example a pulsating direct current having a frequency of
up to 1000 Hz, is applied to the workpiece. The temperature for depositing the chromium may be 45° C. to
95° C., in particular about 55° C. The duration of deposition is selected depending on the desired thickness
of the structured hard chrome layers, the thickness of said layer increasing as the duration of said
deposition increases.
In a preferred embodiment of the present invention, a current density of 20 A/dm 2 to 200 A/dm 2 is used.
Thus, particularly favourable structures of the hard chrome layer are obtained. The higher the current
density is selected to be, the more dense the protruding parts of the structured hard chrome layer will
become.
The cathodic current yield in the production of the structured hard chrome layer according to the method of
the invention is 12% or less. If the current yield is higher, the desired structure of the hard chrome layer will
not be obtained.
It is possible to deposit a plurality of layers on the workpiece, wherein the above-mentioned structured hard
chrome layers and layers formed by conventional electrolytes can be deposited on one another in an
alternating manner. For example, first the structured hard chrome layer obtained by the method according
to the invention can be applied to the workpiece, and then a layer selected from a conventional chromium
layer, a black chromium layer, a copper layer, a nickel layer or a tin layer, may be deposited thereon.
Further, a conventional chromium, copper and/or nickel layer may be deposited first on the workpiece, and
then the hard chrome layer described in more detail above may be deposited thereon.
Further coatings which do not contain chromium, such as copper, nickel, tin, zinc, ceramics, plastics, solid
lubricants, dyes, may be deposited directly onto the hard chrome layer obtained by the method according to
the invention.
A further object of the present invention is a structured hard chrome layer of the type obtained by the
method according to the invention as described in more detail above.
In contrast to the hard chrome layers of the prior art, which have a pronounced spherical laminar structure,
the structured hard chrome layer has a cup-shaped and/or labyrinth-like and/or column-shaped structure.
The structured hard chrome layer according the invention has the advantages mentioned in connection with
the method according to the invention.
The structured hard chrome layer according to the invention may be used for coating a multitude of
workpieces, for example piston rings, cylinders, pistons, bolts, camshafts, seals, composite materials,
valves, bearings for protection against wear and for reduction of friction, pressure cylinders for improved
wetting with dyes, embossing rollers for improved deep-drawing processes in the automobile industry, in
solar technology, for decorative purposes, in medical technology, in micro-engineering and in
microelectronics.
A further object of the present invention is an electrolyte, containing
*
o (a) a Cr (VI) compound in an amount corresponding to 50 g/l to 600 g/l of chromic acid anhydride,
o (b) 0.5 g/l to 10 g/l of sulphuric acid,
o (c) 1 g/l to 20 g/l of aliphatic sulphonic acid comprising 1 to 6 carbon atoms, and
o (d) 10 g/l to 200 g/l of at least one compound forming a dense cathode film, said compound being
selected from among ammonium molybdate, alkali molybdate and alkaline earth molybdate, ammonium
vanadate, alkali vanadate and alkaline earth vanadate, and ammonium zirconate, alkali zirconate and
alkaline earth zirconte.
for carrying out the method according to the invention.
Said electrolyte may be used, in particular, for producing the structured hard chrome layers described in
more detail above on workpieces.
The present invention shall be explained in more detail in the following examples with reference to the
figures, but without being limited thereto.
FIGS. 1 to 8 show photographs corresponding to the hard chrome layers of examples 1 to 8.

EXAMPLE 1
A conventional chromium electrolyte having the following basic composition was prepared:
* Chromic acid anhydride CrO 3 250 g/l

* Sulphuric acid H 2 SO 4 2.5 g/l
A product component is introduced into the electrolyte after conventional pre-treatment and is coated for
30 minutes at 55° C. with 41 A/dm 2 .
The product component coated under these conditions comprises a conventional, glossy and uniformly
structured chromium layer after treatment, cf. FIG. 1.
EXAMPLE 2
100 g/l of ammonium molybdate (NH 4 ) 6 Mo 7 O 24 .4H 2 O and 4 g/l of methane sulphuric acid are
additionally added to the electrolyte of Example 1. A product component is coated under the conditions
described in Example 1. The product component thus described comprises a structured chromium layer after
treatment. Said chromium layer has a glossy appearance on the protruding surface regions (supporting
portion), and a brown cathode film or barrier layer is obtained in the recesses of the structure (FIG. 2).
EXAMPLE 3
A product component is coated under the conditions of Example 2. However, instead of working with a
coating current density of 40 A/dm 2 , 20 A/dm 2 are used.
The product component thus coat comprises a structured chromium layer after treatment. The proportion of
the protruding, glossy surface areas (supporting portion) is smaller and the proportion of recessed regions is
greater by comparison with the structured layer of Example 2 (FIG. 3).
EXAMPLE 4
A product component is coated under the condition of Example 2. However, instead of working with a
coating current density of 40 A/dm 2 60 A/dm 2 are used.
The product component coated in this manner comprises a structured chromium layer after treatment. The
proportion of the protruding, glossy surface regions (supporting portion) is greater and the proportion of
recessed areas is smaller by comparison with the structured layer of Example 2 (FIG. 4).
EXAMPLE 5
A product component is coated under the conditions of Example 2. The product component coated in this
manner comprises a structured chromium layer after treatment. In a conventional chromium electrolyte of
Example 1, coating is now continued on said structured chromium layer for 120 minutes using chromium at
55° C. and 50 A/dm 2 . The product component coated in this manner exhibits a considerable increase in
structural height as compared to Example 2 (FIG. 5).
This graded layer has, on its surface, metallurgic properties like conventional chromium and is structured in
addition.
The advantage of this laminar structure results from the fact that the profile height of the laminar structure
can be varied over a wide range, which is limited by the slow speed of growth of layers in the exclusive
deposition according to Examples 2-4.
EXAMPLE 6
A product component is coated according to the conditions of Example 2. The product component coated in
this manner comprises a structured chromium layer after treatment. A black, chromium oxide-containing
layer is then deposited on this structured chromium layer in a conventional black-chromium electrolyte.
The product component coated in this manner has a uniform, deep-black surface with a very high index of
light refraction (FIG. 6).
EXAMPLE 7
A product component is coated according to the conditions of Example 2. The product component coated in
this manner comprises a structured chromium layer after treatment. In a conventional tin electrolyte, a tin
layer is then deposited on this structured chromium layer, with a thickness sufficient to fill up the recesses
of the structured chromium layer with tin.
The product component coated in this manner has a surface, which, in addition to a high resistance to wear
also possesses a very good sliding properties (FIG. 7).
EXAMPLE 8
A product component is coated according to the conditions of Example 1 with a conventional chromium
layer.
Subsequently, a structured chromium layer is deposited on the chromium layer of Example 1 under the
conditions of Example 2.
The structured chromium layer represents a lead-in layer for the conventional chromium layer and,
depending on the tribological application, leads to an improvement of the laminar system (FIG. 8).
Arvinda Kumar
R-9/303 Sector-9
Rajnagar Ghaziabad
NCR India 201002
+919818004652
1. A method of etching a top and bottom chrome layer of a chrome-copper-chrome conductor array
deposited on a glass plate comprising:
applying a layer of photoresist containing the desired conductor pattern on the surface of said chrome-
copper-chrome layers,
contacting the upper chrome layer with an acidic aqueous etchant composition containing water, an
inorganic acid, and at least one thiourea compound selected from the group of thiourea, substituted
thiourea, and mixtures thereof, and rinsing off the acidic etchant,
contacting the exposed copper layer with an acid etch to strip the surface of said copper to conform to said
conductor pattern, and rinsing off the acid etch, and
contacting the lower chrome surface with the same acidic etchant as said upper surface, and rinsing off the
acidic etchant.
2. The method of claim 1 wherein water is the rinsing material.
3. The method of claim 2 wherein the photoresist material is a positive photoresist material.
4. The method of claim 1 wherein the contacting time on the upper and lower chrome layers is carried out
for about 10 seconds to about 10 minutes, and the temperature employed is about 30° to about 90° C.
5. The method of claim 1 wherein the acid used on chrome layers is present in the amount of about 1.0 to
about 20% by weight and the pH of the composition is about 2 or less.
6. The method of claim 1 wherein the acid used on the chrome layers is present in an amount of about 8 to
about 10% by weight based upon the weight of the composition.
7. The method of claim 1 wherein the pH of the etchant used on the chrome layers is about 0 to about 2.
8. The method of claim 1 wherein the pH of the etchant used on the chrome layers is about 0 to about 1.
9. The method of claim 1 wherein the acid in the acidic aqueous etchant composition is selected from the
group of hydrofluoric acid, hydrochloric acid, phosphoric acid, sulfuric acid or mixtures thereof.
10. The method of claim 1 wherein said acid in the acidic aqueous etchant composition is sulfuric acid.
11. The method of claim 1 wherein the amount of said thiourea compound is about 1 to about 10% by
weight.
12. The method of claim 1 wherein the amount of said thiourea compound is about 1 to about 3% by weight.
13. The method of claim 1 wherein the thiourea compound is thiourea.
14. The method of claim 13 wherein the acid in the acidic aqueous etchant composition is sulfuric acid.
15. The method of claim 1 wherein the temperature of the acidic aqueous etchant composition used on the
chrome layers is about 30° to 90° C.
16. The method of claim 1 wherein said substituted thiourea compound is selected from the group of
alkylthiourea compounds, phenylthiourea compounds and mixtures thereof.
17. The method of claim 1 wherein chrome-copper-chrome conductor arrays are used in fabrication of gas
panels.
18. The method of claim 1 wherein the acidic aqueous etchant composition consists essentially of water,
about 8 to about 10% by weight of sulfuric acid, and about 1 to about 10% by weight of at least one thiourea
compound selected from the group of thiourea, substituted thiourea, and mixtures thereof.
20. The method of claim 18 wherein the amount of the thiourea compound is about 1 to about 3% by weight.
21. The method of claim 1 wherein the acidic aqueous etchant composition consists essentially of about 1.5
to about 20% by weight of an acid selected from the group of hydrofluoric acid, hydrochloric acid,
phosphoric acid, sulfuric acid, and mixtures thereof, about 1 to about 10% by weight of at least one thiourea
compound selected from the group of thiourea, substituted thiourea, and mixtures thereof; and wherein the
pH of the composition is about 2 or less.
23. In a process of fabricating gas panels in which layers of a chromium/copper/chromium conductor array
are formed on glass plates in which successive layers of chromium, copper and chromium are removed by
selective etching through patterned resist masks, the improvement which comprises, contacting the upper
chrome layer with an acidic aqueous etchant composition containing water, an inorganic acid, and at least
one thiourea compound selected from the group of thiourea, substituted thiourea, and mixtures thereof,
rinsing off the acidic etchant, contacting the exposed copper layer with an acid etch to strip the surface of
the copper to conform to the pattern of the resist mask, rinsing off the acid etch, contacting the lower
chrome surface with the same acidic etchant as the said upper surface, and rinsing off the acidic etchant.
24. In a process of fabricating gas panels in which layers of a chromium/copper/chromium conductor array
are formed on a cermet layer on a glass plate in which successive layers of cermet, chromium, copper and
chromium are removed by selective etching through patterned resist masks, the improvement which
comprises, contacting the upper chrome layer with an acidic aqueous etchant composition containing water,
an inorganic acid, and at least one thiourea compound selected from the group of thiourea, substituted
thiourea, and mixtures thereof, rinsing off the acidic etchant, contacting the exposed copper layer with an
acid etch to strip the surface of the copper to conform to the pattern of the resist mask, rinsing off the acid
etch, contacting the lower chrome surface with the same acidic etchant as said upper surface, and rinsing
off the acidic etchant.
Description:
TECHNICAL FIELD
The present invention relates to compositions suitable for use as etchants for etching composite chrome
layers. In particular, the present invention is concerned with acidic etching compositions especially
applicable in etching composite chrome-copper- chrome conductor arrays deposited on glass plates and used
in process of fabricating gas panels.
In the manufacture and fabrication of gas panels many different types of materials are used, and in
numerous types of such construction very small and very thin parallel electrical conductors are deposited on
substrates, and a pair of such substrates are disposed on opposite sides of a chamber filled with an
illuminable gas with one set of the parallel electrical conductors extending orthogonally with respect to the
other set of parallel electrical conductors to define coordinate intersections. A given one of the parallel
electrical conductors from each set is energized with electrical signals to ignite the region of the illuminable
gas around a selected coordinate intersection. The electrical conductors are made as narrow and thin as
desired in order to obtain a greater number of coordinate intersections per square inch of the gas panel.
Often times however, commercial gas panels entail, in part, the use of a conductor array fabricated by
applying to a glass plate, a chrome layer, followed by a copper layer, followed by another chrome layer.
Also, sometimes a cermet layer is placed between the glass plate substrate and bottom chrome layer. Next,
a photoresist composition is applied so that selected areas of the chrome/copper/ chrome/cermet layers
can be removed to provide the desired electrical connections on the substrates.
Glass is deposited over the top chrome layer to ensure separation of the parallel lines. The copper layer
provides electrical conductivity. The bottom chrome layer is applied to ensure adequate adhesion between
the copper and the glass or cermet. The cermet in conjunction with subsequently applied material acts as a
resistor in the final product.
The etching of the chrome layers has been carried out employing etchant compositions having a high pH,
such as aqueous compositions containing KMnO 4 . The use of aqueous etchant compositions having a high
pH is not entirely satisfactory, since KMnO 4 tends to attack the photoresist to some extent as well as the
chrome layers.
Further, commercially available positive photoresist materials such as those based on phenolic-
formaldehyde novalak polymers are not resistant to the highly basic etchant compositions employed to etch
the chrome, and, accordingly will not protect the non-etched areas.
Therefore, the ability to employ a positive photoresist is advantageous for the reason that a positive resist is
less sensitive to dirt or other contaminants than is a negative photoresist, because only the exposed areas of
a positive photoresist are developed and etched away. Consequently, if dirt or another contaminant matter
is present, it will remain on the unexposed portion, and will not play a significant part in regard to
formation of defects. By contrast, with a negative photoresist, the exposed areas are cured and the
unexposed areas are etched away.
In addition, the ability to use a positive photoresist makes it possible to employ a single coating to prepare
several different circuits by exposing, developing and etching the required surface and then repeating the
steps as many times as needed. Furthermore, positive resists provide sharper image resolution as compared
to negative resists, since the desired image does not swell and remains unchanged during the development
with the particular solvent. Further still, the unexposed positive photoresist can be readily removed when
desired by simple chemical solvents which include N-methyl-2-pyrrolidone for many commercially available
positive resists and/or reexposed to suitable light, and then removed with the same solution employed to
develop the circuitry. Additionally, aqueous solutions that are highly basic such as sodium hydroxide can
also effectively remove the photoresist.
However, the various commercially available positive photoresists, such as the methacrylate polymers,
necessitate an etchant for the underlying chrome which is on the acidic side. Although certain acidic
etchants have been suggested for chrome, they are not entirely satisfactory. For instance, the etching with
various prior acidic etchants is very slow at the start but then accelerates very rapidly forming or generating
relatively large amounts of gas which are uncontrollable and cause the formation of bubbles. This is not
suitable, especially for fine line circuitry. Moreover, sometimes the chrome surface is not even etched at all
in such acidic etchants which may be possible due to passivation of the chrome surface.
It has previously been found that mixtures of glycols and diluted HCl etch chromium at ambient
temperatures. But, when etching the lower chromium layer, the exposed edges of the top chromium layer
etch during the relatively longer times needed to etch the lower layer so that undercutting of the top layer
occurs. This in turn results in a portion of the copper being exposed at the top edges and ends of the
conductor lines, and this could render the structure inoperative upon subsequent or further fabrication.
It has also been found that a concentrated HCl mixture of about 50% or more by volume provides an etch
time for the lower chromium layer which sufficiently minimizes the undercutting of the top chromium layer;
however, these concentrated mixtures attack the cermet, when used, and cause unacceptable changes in its
resistivity.
These problems of undercutting of the top chromium layer and changes in the resistivity of the cermet have
been minimized by employing the invention disclosed in U.S. Pat. No. 4,160,691 to Abolafia, et al. wherein
certain concentrated HCl compositions are employed at temperatures from about 50° to about 95° C.
Although, the invention disclosed and described in U.S. Pat. No. 4,160,691 does minimize undercutting of
the top chromium layer and the changes in resistivity of the cermet occasioned by other acidic
compositions, it is still not entirely satisfactory. The compositions are still in need of improvement with
respect to pH stability during use, and improvement with respect to storage stability over relatively long
periods of time would still be useful.
Most importantly, however, is the fact that etching the top and bottom chrome layers of a chrome-copper-
chrome conductor array deposited on a glass plate employing prior art etchants such as potassium
permanganate entailed the numerous steps of: contacting the upper chrome layer with potassium
permanganate and washing off excess permanganate with water; contacting the intermediate copper layer
with ammonium persulfate and washing off the persulfate with water; and contacting the lower chrome
layer with potassium permanganate. However, in the case of the lower chrome layer, it is necessary to
remove the manganese component of the potassium permanganate etchant even after the rinse with water,
by using an oxalic acid rinse followed by a water rinse. Thereafter, a second etching step using more
potassium permanganate was required, and this was followed by a final water rinse.
It is believed that the lower chrome layer next to the glass or cermet has a higher oxide content than the
upper chrome layer and is more difficult to etch. Therefore to ensure thorough etching, it was necessary to
remove the manganese component of the potassium permanganate from the lower chrome layer with oxalic
acid, and conduct another or second etching step on the lower chrome layer with additional potassium
permanganate.
DISCLOSURE OF THE INVENTION
The present invention provides an etchant composition which is acidic and which is capable of etching a top
and bottom chrome layer of a chrome-copper- chrome conductor array deposited on a glass plate in a
simpler, more controllable, less expensive, and faster way than prior art processes employing potassium
permanganate.
This is accomplished by applying a layer of photoresist containing the desired conductor pattern on the
surface of chrome-copper- chrome layers, contacting the upper chrome layer with an acidic aqueous
etchant composition containing water, an inorganic acid, and at least one thiourea compound selected from
the group of thiourea, substituted thiourea, and mixtures thereof, rinsing off the acidic etchant; contacting
the exposed copper layer with an acid etch to strip the surface of said copper to conform to the conductor
pattern, rinsing off the acid etch; contacting the lower chrome surface with the same acidic etchant as used
on said upper surface; and rinsing off the acidic etchant.
By using the compositions in the process of the present invention, the second etching step of the lower
chrome layer, which is required in the permanganate process is eliminated, and it is not necessary to
employ the oxalic acid step because the lower chrome layer is thoroughly etched in a single etch with the
compositions of the invention.
The compositions of the present invention are pH stable during use and over long periods of time and can be
stored without detrimental effect to the composition, for relatively long periods of time. Further, with the
etchant compositions of the invention, bubble formation is substantially eliminated. Moreover, excellent
resolution is achieved with the etchant compositions of the invention. The invention also makes it possible
to employ positive photoresists which are commercially available since these are resistant to the etchant
compositions of the invention. Moreover, the present invention provides for uniform etching of the
chromium.
In particular, the present invention is concerned with a method for etching a top and bottom chrome layer
of a chrome-copper- chrome conductor array deposited on a glass plate comprising:
applying a layer of photoresist containing the desired conductor pattern on the surface of said chrome-
copper- chrome layers,
contacting the upper chrome layer with an acidic aqueous etchant composition containing water, an
inorganic acid, and at least one thiourea compound selected from the group of thiourea, substituted
thiourea, and mixtures thereof, and rinsing off the acidic etchant,
contacting the exposed copper layer with an acid etch to strip the surface of said copper to conform to the
conductor pattern, and
rinsing off the acid etch, and
contacting the lower chrome surface with the same acidic etchant as said upper surface, and rinsing off the
acidic etchant.
The invention is further in particular concerned with improvements in the process of forming gas panels, and
reference is made as an incorporation by reference to U.S. Pat. Nos. 3,804,609 and 3,837,724 as typical
processes in which the aqueous acidic etching compositions can be used as a step in forming such panels.
Furthermore, the invention is concerned with certain compositions which consist essentially of water, about
1 to about 10% by volume of sulfuric acid, and about 1 to about 10% by weight of thiourea and/or
substituted thiourea.
The acidic aqueous compositions of the invention contain an inorganic acid and the acid employed under
conditions of use must be capable of etching chrome. Examples of inorganic acids are hydrofluoric acid,
hydrochloric acid, phosphoric acid, and preferably sulfuric acid. Mixtures of acids can be used if desired.
One particular advantage of the invention is that the invention makes it possible to provide an etchant
composition for chromium which does not require hydrochloric acid. Also, preferably, the compositions of
the invention should be substantially, if not entirely, free from nitric acid since it tends to attack copper,
which is present beneath the top chrome layer in the articles treated by the compositions of the invention.
The acid is present in the composition in amounts sufficient to etch the chrome, and these amounts are
usually from about 1.0 to about 20% by weight of the aqueous composition. Preferred amounts of the acid is
3 to 10% by volume at a temperature from about 30° to 90° C., preferably 30° to 70° C. and this renders the
pH of the composition less than (<2.5); preferably, between 0 and 2, and most preferably between 0 and 1.
In addition, the compositions of the present invention must include thiourea or at least one substituted
thiourea or mixtures thereof. Examples of some substituted thiourea compounds include alkylthiourea
compounds such as 1, 3-dimethylthiourea, 1, 3-diethylthiourea, 1, 3-diisopropylthiourea, and 1, 3-
dibutylthiourea; allylthiourea; diphenylthiourea; and ethylenethiourea. The preferred compound employed
is thiourea. The amount of the thiourea compound employed is usually about 1 to about 10% by weight, and
preferably about 2 to about 5% by weight.
The compositions of the present invention are especially suitable for etching chrome and for selectively
etching chrome layers without affecting underlying copper, without affecting positive photoresist materials,
and without significantly affecting the resistivity of cermet, which may also be present beneath the chrome.
The etching can be achieved by immersing the particular article to be etched in a bath of the composition
and maintaining the material to be etched in contact with the composition for about 10 seconds to about 10
minutes, and preferably for about 30 seconds to about 3 minutes. The composition is capable of etching
chromium at a rate of 2000 ? per minute, and at one fifth the cost per unit batch over the prior art
permanganate process.
The acidic aqueous compositions of the invention are approximately one-fifth less expensive than the
potassium permanganate etch. Moreover the pH of the acidic aqueous compositions is not critical within the
acid range (i.e. 0 to 7), and with a constant thiourea concentration, the etching speed varies with the acid
concentrations. Further, in contrast to the etching process using potassium permanganate, the photoresist
layer in the invention process requires either no baking or a shorter baking time because it is not attacked
by the acid etch. The acidic solution can be applied using spray or immersion techniques for etching and,
due to the less expensive cost of the acidic aqueous compositions together with elimination of the oxalic
acid rinse and the second potassium permanganate etching step required in the prior art process, the speed
of the etching in the present invention is much faster and the cost of the etching in the present invention,
especially as part of the gas panel fabricating process, is substantially lower than that in the potassium
permanganate process.
The compositions of the present invention are employed generally at temperatures of about 30° C. up to
about the boiling point of the compositions, and preferably no higher than about 90° C. The preferred
temperatures are about 30° to about 70° C. The time and temperature of the etching are inversely related.
For example, at the lower temperatures longer immersion times of up to about 10 minutes are employed for
etching away about 1,000 ? of chromium. Further, the time is somewhat related to the thickness of the
material to be etched away.
A particular type of article etched according to the invention is a glass plate on top of which is a first layer
of about 1,600 ? chromium, followed by a layer of about 25,000 ? of copper, on top of which is another 1,600
? chromium layer. If desired, a cermet, such as a silicon monoxide cermet material can be placed between
the glass plate and the first chromium layer.
A typical example of a suitable cermet is obtained from firing a composition containing chrome and silicon
monoxide.
The following example is presented to further illustrate the invention in a nonlimiting way.
EXAMPLE I
An etch solution is prepared by dissolving sufficient concentrated sulfuric acid (i.e. about 98%
concentration) in water to obtain 3 to 10% by volume of the acid in water and thiourea is added so that it is
from 3 to 10% by weight of the deionized water.
A glass plate having a 1,600? layer of chrome, on top of which is a 25,000 ? layer of copper, on top of which
is another 1,600? layer of chrome on top of which is a layer of photoresist containing the desired conductor
pattern is immersed in the etch solution. The solution is at a temperature between 30° to 70° C. The top
chrome layer of 1,600? is etched away in about two minutes, and the acidic solution is washed off with
deionized water. A predetermined portion of the copper is then etched away with an ammonium persulfate
solution, and the bottom chrome layer is etched away with the same solution used to etch away the upper
layer, after washing off the ammonium persulfate with deionized water. There is only minimum
undercutting of the top chromium during the etching of the bottom chromium layer.
Arvinda Kumar
R-9/303 Sector-9
Rajnagar Ghaziabad
NCR India 201002
+919818004652
1. A chrome plated part comprising a substrate having a crack-free chrome layer on a surface thereof, the
crack-free chrome layer having compressive residual stress of 100 MPa or more and being formed by
electroplating.
2. A chrome plated part according to claim 1, wherein the chrome layer has a crystal grain size of 9 nm or
more.
3. A chrome plated part according to claim 2, wherein the crystal grain size of the chrome layer is less than
16 nm.
4. A chrome plated part according to claim 1, wherein the crack-free chrome layer is a lower chrome layer
and the chrome plated part further comprises a cracked upper chrome layer which is formed on the lower
chrome layer by electroplating.
5. A chrome plated part according to claim 4, wherein the upper chrome layer has tensile residual stress.
6. A chrome plated part according to claim 5, wherein the upper chrome layer has a crystal grain and the
crystal grain has a size less than 9 nm.
7. A chrome plated part according to claim 4, further comprising at least one intermediate chrome layer
which is formed between the lower chrome layer and the upper chrome layer by electroplating.
8. A chrome plated part according to any one of claims 1, 4 and 7, further comprising an oxide film
containing Cr2 O3 as an outermost layer thereof.
9. A chrome plated part comprising a substrate having a crack-free chrome layer on a surface thereof, the
crack-free chrome layer having compressive residual stress of 150 MPa or more and being formed by
electroplating.
10. A chrome plated part according to claim 9, wherein the crack-free chrome layer has a crystal grain size
of 9 nm or more.
11. A chrome plated part according to claim 10, wherein the crystal grain size of the crack-free chrome
layer is less than 16 nm.
12. A chrome plated part comprising:
a substrate having a surface; and
a chrome layer deposited on the surface of the substrate by electroplating, the chrome layer having
compressive residual stress of 100 MPa or more.
13. A chrome plating method comprising the step of conducting electroplating of a work in a chrome plating
bath by application of a pulse current, the chrome plating bath containing organic sulfonic acid, to thereby
deposit a crack-free chrome layer on a surface of the work, the crack-free chrome layer having compressive
residual stress of 150 MPa or more.
14. A chrome plating method comprising the step of conducting electroplating of a work in a chrome plating
bath by application of a pulse current, the chrome plating bath containing organic sulfonic acid, to thereby
deposit a crack-free chrome layer on a surface of the work, the crack-free chrome layer having compressive
residual stress of 100 MPa or more.
15. A chrome plating method according to claim 14 or 13, wherein the crack-free chrome layer is formed to
have a crystal grain size of from 9 nm to less than 16 nm by adjusting a waveform of the pulse current.
16. A method for producing a chrome plated part, comprising the steps of:
conducting the chrome plating method of claim 14;
polishing the crack-free chrome layer on the surface of the work; and
conducting heat oxidation, to thereby form an oxide film containing Cr2 O3 on a surface of the crack-free
chrome layer.
17. A method according to claim 16, wherein the heat oxidation is conducted under the same conditions as
conditions of a baking process.
18. A method according to claim 16, wherein the heat oxidation is conducted by high-frequency heating.
19. A chrome plating method according to claim 14, further comprising the step of conducting, after the
pulse plating, electroplating of the work in the same chrome plating bath as the chrome plating bath for the
pulse plating, by one of adjustment of a waveform of the pulse current and application of a direct current,
to thereby deposit a cracked upper chrome layer on the crack-free chrome layer.
20. A chrome plating method according to claim 14, further comprising the steps of:
conducting, after the pulse plating, electroplating of the work in the same chrome plating bath as the
chrome plating bath for the pulse plating, by one of adjustment of a waveform of the pulse current and
application of a direct current, to thereby deposit an intermediate chrome layer on the crack-free chrome
layer; and
conducting electroplating of the work in the same chrome plating bath as the chrome plating bath for the
pulse plating, by one of adjustment of the waveform of the pulse current and application of the direct
current, to thereby deposit a cracked upper chrome layer on the intermediate chrome layer.
21. A chrome plating method according to claim 19 or 20, wherein the chrome layers are deposited by
continuous operation by continuously moving the work in the chrome plating bath.
22. A chrome plating method according to claim 19 or 20, wherein the chrome layers are deposited by
batchwise operation by immersing the work in the chrome plating bath.
23. A method for producing a chrome plated part, comprising the steps of:
conducting the chrome plating method of claim 19 or 20;
polishing the upper chrome layer formed on the crack-free chrome layer on the surface of the work; and
conducting heat oxidation, to thereby form an oxide film containing Cr2 O3 on a surface of the upper
chrome layer.
24. A method according to claim 23, wherein the heat oxidation is conducted under the same conditions as
conditions of a baking process.
25. A method according to claim 23, wherein the heat oxidation is conducted by high-frequency heating.
26. A chrome plating method comprising the steps of:
providing a substrate having a surface; and
depositing a chrome layer on the surface of the substrate by electroplating so that the chrome layer has
compressive residual stress of 100 MPa or more.
Description:
The present invention relates to chrome plated parts comprising substrates having industrial chrome plating
applied on the surfaces thereof. The present invention also relates to a chrome plating method and a
production method for obtaining such parts.
Chrome plating, especially hard chrome plating, provides a hard metallic coating (i.e., a chrome layer)
having a low coefficient of friction. Therefore, chrome plating has been widely used as industrial chrome
plating for parts which are required to have high wear resistance.
With respect to general-purpose hard chrome plating, a chrome layer formed on a metallic substrate
contains many cracks reaching the substrate, called channel cracks. Such a chrome layer enables a corrosive
material to migrate into the metallic substrate and cause corrosion. This leads to formation of red rust when
the substrate is made of steel.
In producing chrome plated parts, generally, a plated substrate is subjected to polishing, such as buffing, so
as to provide a smooth surface. It is known that during polishing, cracks in a chrome layer become clogged
due to the occurrence of plastic flow over the surface of the chrome layer. Therefore, in producing general-
purpose chrome plated parts, after polishing, no special measures have been taken to prevent rusting.
However, when a chrome layer is subject to thermal hysteresis, contraction of the chrome layer occurs. In
this case, cracks which have been clogged due to plastic flow in the chrome layer are caused to open.
Consequently, parts which are used at temperatures higher than room temperature (for example, at 120° C.
for 100 hours or more) are likely to suffer a lowering in corrosion resistance.
As a countermeasure, it has been attempted to conduct nickel plating or copper plating as a pretreatment,
to thereby form a lower layer having a thickness almost equal to that of a chrome layer to be formed, and
conducting hard chrome plating on the lower layer. However, in this countermeasure, a plating process must
be conducted in two steps, leading to low productivity and high process costs.
As another countermeasure, it has been proposed to conduct chrome plating by using two different plating
baths, to thereby deposit two chrome layers having different crystal orientations, thus preventing the
formation of cracks reaching the substrate [reference is made to, for example, Unexamined Japanese
Patent Application Public Disclosure (Kokai) No. 4-350193]. However, this countermeasure also requires a
two-step plating process.
Further, there is a method of conducting electroplating with a pulse current, so-called pulse plating, so as
to obtain a crack-free chrome layer [reference is made to, for example, Unexamined Japanese Patent
Application Public Disclosure (Kokai) No. 3-207884]. However, the chrome layer formed simply by pulse
plating is subject to tensile residual stress. This leads to the formation of large cracks in the chrome layer
due to the application of heat.
Further, there is a method of conducting pulse plating in a Sargent bath by application of an irregular pulse
current, to thereby obtain a crack-free decorative chrome layer [reference is made to, for example,
Examined Japanese Patent Application Publication (Kokoku) No. 43-20082]. The chrome layer obtained by
this method has low (or no) stress. However, the obtained chrome layer has a stress gradient (as the
thickness of the chrome layer becomes large, the value of stress shifts from a side of compressive stress
toward a side of tensile stress). Therefore, average compressive stress in the chrome layer is undesirably
low. Consequently, when the above-mentioned chrome layer is used as a lower layer and a cracked chrome
layer is formed as an upper layer by plating on the lower chrome layer, the lower chrome layer is subject to
tensile stress from the upper chrome layer, so that propagation of cracks through the upper chrome layer to
the lower chrome layer occurs. Further, in the chrome plating bath in Kokoku No. 43-20082, average
compressive residual stress can be increased only to a level as low as 100 MPa, even by controlling the
waveform of an applied pulse current, a bath temperature and a current density.
In view of the above, the present invention has been made. It is an object of the present invention to
provide chrome plated parts which maintain excellent corrosion resistance even when the chrome plated
parts are subject to thermal hysteresis. It is another object of the present invention to provide a chrome
plating method and a production method for efficiently obtaining such chrome plated parts.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a chrome plated part comprising a substrate having a
crack-free chrome layer applied on a surface thereof. The crack-free chrome layer has compressive residual
stress and is formed by plating.
In the chrome plated part of the present invention in which a crack-free chrome layer having compressive
residual stress is formed on a surface of the substrate, due to the compressive residual stress in the chrome
layer, no formation of cracks in the chrome layer occurs. Therefore, the chrome layer maintains a crack-
free structure. Consequently, the chrome plated part maintains excellent corrosion resistance even when it
is subject to thermal hysteresis.
When compressive residual stress in the chrome layer is too low, the compressive residual stress changes to
tensile residual stress due to the occurrence of thermal hysteresis. This leads to the formation of cracks in
the chrome layer. Therefore, it is preferable for the compressive residual stress in the crack-free chrome
layer to be 100 MPa or more.
Generally, when a chrome layer is subject to thermal hysteresis, the formation of cracks is likely to occur
due to contraction of the chrome layer. This contraction is affected by the amount of lattice defects
present in crystal grain boundaries in the chrome layer. Therefore, contraction of the chrome layer due to
thermal hysteresis can be suppressed by suppressing the amount of lattice defects, that is, by increasing a
crystal grain size and decreasing the length of a crystal grain boundary (the length of a crystal grain
boundary is in inverse proportion to a crystal grain size). Therefore, in the chrome plated part of the
present invention, it is preferred that the crystal grain size of the crack-free chrome layer be 9 nm or more.
The crystal grain size of a chrome layer formed by general-purpose hard chrome plating is as small as about
6 nm. The above-mentioned crystal grain size of the chrome layer in the present invention is much larger
than this size. Therefore, the chrome layer in the present invention contains no cracks even prior to
polishing, and maintains a crack-free structure even when it is subject to thermal hysteresis. Therefore, the
chrome plated part has desired corrosion resistance. When the crystal grain size is too large, a crystal
structure of the chrome layer changes. Therefore, it is preferable for the crystal grain size of the crack-free
chrome layer to be less than 16 nm.
In the chrome plated part of the present invention, the crack-free chrome layer may be a lower chrome
layer and the chrome plated part may further comprise a cracked upper chrome layer which is formed or
applied on the lower chrome layer by plating. In this case, the hardness of the upper chrome layer can be
increased to a maximum level. This improves wear resistance of the chrome plated part. Further, cracks in
the upper chrome layer serve as oil sumps for holding lubricating oil, leading to suppression of sliding
resistance.
The chrome plated part may further comprise at least one intermediate chrome layer which is formed
between the lower chrome layer and the upper chrome layer by plating. When an intermediate chrome
layer is provided, direct propagation of cracks through the upper chrome layer to the lower chrome layer
can be suppressed. Therefore, corrosion resistance of the chrome plated part can be stably maintained.
The chrome plated part may further comprise an oxide film containing Cr 2 O 3 as an outermost layer
thereof. In this case, the chrome layer itself has high corrosion resistance, so that formation of white rust
can be prevented.
The present invention also provides a chrome plating method comprising the step of conducting
electroplating of a work in a chrome plating bath by application of a pulse current, the chrome plating bath
containing organic sulfonic acid, to thereby deposit a crack-free chrome layer on a surface of the work. The
crack-free chrome layer has compressive residual stress.
In the chrome plating method of the present invention, by adjusting a pulse waveform of an applied current
which alternates between a maximum current density and a minimum current density, the compressive
residual stress and crystal grain size of a chrome layer can be easily controlled. Therefore, it is possible to
obtain a chrome layer having a compressive residual stress of 100 MPa or more and a crystal grain size of
from 9 nm to less than 16 nm.
In the chrome plating method of the present invention, the above-mentioned chrome layer may be formed
as a lower chrome layer and the above-mentioned upper chrome layer or the above-mentioned intermediate
and upper chrome layers may be formed on the lower chrome layer. In this case, after the chrome layer is
deposited as a lower chrome layer by using the pulse plating, electroplating of the work is conducted in the
same chrome plating bath as the chrome plating bath for the pulse plating, by one of adjustment of a
waveform of the pulse current and application of a direct current, to thereby deposit the upper chrome
layer or intermediate chrome layer efficiently.
The chrome layers may be deposited by continuous operation by continuously moving the work in the
chrome plating bath or may be deposited by batchwise operation by immersing the work in the chrome
plating bath.
Further, the present invention provides a method for producing a chrome plated part, comprising the steps
of: conducting the above-mentioned chrome plating method for the two or more than three layers; polishing
the upper surface of the work; and conducting heat oxidation, to thereby form an oxide film containing Cr 2
O 3 on a surface of the chrome layer.
When the upper chrome layer containing cracks is formed by the chrome plating method of the present
invention, the cracks in the upper chrome layer become clogged during polishing due to the above-
mentioned plastic flow in the chrome layer. Although the cracks are caused to open again due to heat
oxidation after polishing, the chrome plated part has sufficient corrosion resistance for preventing
formation of red rust, because the crack-free lower chrome layer is present on the substrate. In addition,
since an oxide film containing Cr 2 O 3 is present as the outermost layer of the chrome plated part,
corrosion of the chrome layer itself can be suppressed, thus preventing formation of white rust.
In the method of the present invention for producing a chrome plated part, the method of heat oxidation is
not particularly limited. For example, heat oxidation can be conducted under the same conditions as
conditions of a general-purpose baking process or by high-frequency heating. With respect to the general-
purpose baking process, Federal Specification QQ-C-320a (1967. 7. 25) requires that when steel having a
hardness of HRC 40 or more is used as a substrate, the baking process be conducted at 191±14° C. for 3
hours or more. By conducting heat oxidation under the above-mentioned conditions, an oxide film
containing Cr 2 O 3 is formed on a surface of a substrate. As a method of heat oxidation by high-frequency
heating, for example, a substrate is held at a temperature as high as about 400° C. for a short period of
time of from several seconds to several tens of seconds.
The foregoing and other objects, features and advantages of the present invention will be apparent from
the following detailed description and appended claims taken in connection with the accompanying
drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of cross section showing a surface structure of a chrome plated part
according to a first embodiment of the present invention.
FIG. 2 is a graph showing an example of a waveform of a pulse current in a chrome plating process for
obtaining the chrome plated part of FIG. 1.
FIG. 3 is a top view schematically showing a structure of a plating apparatus used in the method of the
present invention.
FIG. 4 is a schematic illustration showing a surface structure of a chrome plated part according to a second
embodiment of the present invention.
FIG. 5 is a graph showing an example of a waveform of a pulse current in a chrome plating process for
obtaining the chrome plated part of FIG. 4.
FIG. 6 is a schematic illustration showing a surface structure of a chrome plated part according to a third
embodiment of the present invention.
FIG. 7 is a top view schematically showing a structure of a system including polishing and heating
apparatuses for obtaining the chrome plated part of FIG. 6.
FIG. 8 is a microphotograph showing white rust formed in Examples.
FIG. 9 is a graph showing a relationship between a thickness of plating and residual stress in the chrome
plated part of the present invention.
Hereinbelow, embodiments of the present invention are explained, with reference to the drawings.
FIG. 1 shows a chrome plated part according to a first embodiment of the present invention. The chrome
plated part comprises: a steel substrate M; a crack-free lower chrome layer S 1 formed by plating on a
surface of the substrate M; and a multicracked upper chrome layer S 2 formed by plating on the lower
chrome layer S 1 . The cracks in the chrome layer S 2 are designated by a reference character F. The lower
chrome layer S 1 has a compressive residual stress of 100 MPa or more and has a crystal grain size of from 9
nm to less than 16 nm. The upper chrome layer S 2 has a compressive residual stress less than 100 MPa or a
tensile residual stress and has a crystal grain size less than 9 nm.
In the above-mentioned chrome plated part, the crack-free lower chrome layer S 1 is present below the
upper chrome layer S 2 . Therefore, although the cracks F are present in the upper chrome layer S 2 , a
corrosive material does not migrate into the substrate M, so that a desired corrosion resistance of the
chrome plated part can be ensured. Further, the lower chrome layer S 1 has a predetermined compressive
residual stress and a predetermined crystal grain size, so that the lower chrome layer S 1 maintains a crack-
free structure even when it is subject to thermal hysteresis, to thereby ensure excellent corrosion
resistance of the chrome plated part. In addition, since the upper chrome layer S 2 may contain cracks such
as the cracks F, the hardness of the upper chrome layer S 2 can be increased to a sufficiently high level (900
HV or more), to thereby impart the chrome plated part with sufficient wear resistance. Further, the cracks
F present in the upper chrome layer S 2 serve as oil sumps for holding lubricating oil, which enhances sliding
properties of the chrome plated part.
The chrome layers S 1 and S 2 are formed by a two-step plating process in a chrome plating bath containing
organic sulfonic acid. The two-step plating process comprises plating utilizing a pulse current (hereinafter,
frequently referred to as "pulse plating") and plating utilizing a direct current (hereinafter, frequently
referred to as "general-purpose plating"). An example of a current density pattern of an applied current for
this process is shown in FIG. 2.
As the chrome plating bath containing organic sulfonic acid, it is preferred to use a chrome plating path
described in Examined Japanese Patent Application Publication (Kokoku) No. 63-32874, which has
compositions as shown in Table 1. TABLE 1 Amount (g/L) Component Suitable Preferable Chromic acid 100-
450 200-300 Sulfuric acid 1-5 1.5-3.5 Organic sulfonic acid 1-18 1.5-12 Boric acid 0-40 4-30
Referring to FIG. 2, a zone A indicates a region for the pulse plating for forming the lower chrome layer S 1
and a zone B indicates a region for the general-purpose plating for forming the upper chrome layer S 2 . In
the zone A, the applied current alternates between two current densities, namely, a maximum current
density I U and a minimum current density I L . The maximum current density I U is held for a
predetermined time period T 1 and the minimum current density I L is held for a predetermined time period
T 2 . In the example of FIG. 2, the minimum current density I L is set to zero (off). However, needless to
say, the minimum current density I L may be arbitrarily set to a value between the maximum current
density I U and zero. Further, the values of the time periods T 1 and T 2 may be set as being the same or
different. In the first embodiment, for pulse plating, the maximum current density I U , the minimum
current density I L (I L =0 in this example), the time period T 1 at the maximum current density I U and the
time period T 2 at the minimum current density I L are set to appropriate values, to thereby obtain the
lower chrome layer S 1 (FIG. 1) having a predetermined compressive residual stress and a predetermined
crystal grain size.
FIG. 3 shows an example of an apparatus for obtaining a chrome plated part having the above-mentioned
two chrome layers S 1 and S 2 . In FIG. 3, works (such as piston rods) W are suspended from endlessly
movable hangers 1. A mounting station 2, an alkali electrolytic degreasing tank 3, a plating tank 4, a
cleaning tank 5 and a removing station 6 are arranged in this order below a line of movement of the hangers
1. The plating tank 4 comprises an etching process tank 4A disposed adjacent to the alkali electrolytic
degreasing tank 3 and a plating process tank 4B adjacent to the etching process tank 4A. The plating process
tank 4B contains the above-mentioned chrome plating bath containing organic sulfonic acid.
Separate bus bars 7, 8 and 9 are arranged along the alkali electrolytic degreasing tank 3, the etching process
tank 4A and the plating process tank 4B, respectively. The bus bar 9 extending along the plating process
tank 4B comprises a front bus bar 9A on a side of the etching process tank 4A and a rear bus bar 9B on a side
of the cleaning tank 5. The bus bar 7 corresponding to the alkali electrolytic degreasing tank 3, the bus bar
8 corresponding to the etching process tank 4A and the rear bus bar 9B corresponding to the plating process
tank 4B are connected to direct current sources 10, 11 and 13, respectively. The front bus bar 9A
corresponding to the plating process tank 4B is connected to a pulse current source 12.
The hangers 1 have feeding brushes 14. The feeding brushes 14 are brought into sliding contact with the bus
bars 7, 8, 9A and 9B, so that a current is equally applied from the current sources 10, 11, 12 and 13 to each
of the hangers 1. In each of the alkali electrolytic degreasing tank 3 and the etching process tank 4A, a
plurality of cathodes connected in parallel are provided. The cathodes in the alkali electrolytic degreasing
tank 3 and the cathodes in the etching process tank 4A are designated by reference numerals 15 and 16,
respectively. The plating process tank 4B contains a plurality of anodes 17 corresponding to the front bus
bar 9A, which are connected in parallel, and a plurality of anodes 18 corresponding to the rear bus bar 9B,
which are also connected in parallel. The current sources 10 and 11 apply currents to the corresponding
cathodes 15 and 16, and the current sources 12 and 13 apply currents to the corresponding anodes 17 and
18. In the plating process tank 4B, ammeters 19a and 19b are provided between the anode 17 and the
current source 12 and between the anode 18 and the current source 13, respectively.
In order to conduct a chrome plating process using the above-mentioned apparatus, the works W are
mounted on the hangers 1 in the mounting station 2. The works W are moved successively to the alkali
electrolytic degreasing tank 3 and the etching process tank 4A while being suspended from the hangers 1. In
the alkali electrolytic degreasing tank 3, a degreasing process is conducted while making the works W
anode. In the etching process tank 4A, an etching process is conducted while making the works W anode.
Subsequently, the works W are moved to the plating process tank 4B, where a chrome plating process is
conducted while making the works W cathode.
In the chrome plating process, a current having a pulse waveform, such as that indicated in the zone A of
FIG. 2, is applied from the current source 12 to the works W through the front bus bar 9A and the anodes 17,
to thereby conduct pulse plating. Pulse plating is continued while the feeding brushes 14 of the hangers 1
(from which the works W are suspended) are in contact with the front bus bar 9A. Consequently, the crack-
free lower chrome layer S 1 (FIG. 1) is formed on a surface of each work W. Subsequently, the feeding
brushes 14 of the hangers 1 (from which the works W are suspended) move onto the rear bus bar 9B, and
general-purpose plating is conducted by application of a direct current from the current source 13 to the
works W through the rear bus bar 9B and the anodes 18. General-purpose plating is continued while the
feeding brushes 14 of the hangers 1 (from which the works W are suspended) are in contact with the rear
bus bar 9B. Consequently, the multicracked chrome layer S 2 having the cracks F is formed on the lower
chrome layer S 1 in a superimposed manner as shown in FIG. 1. Thereafter, the works W are cleaned with
water in the cleaning tank 5 and moved to the removing station 6, where the works W are removed from the
hangers 1.
In the above-mentioned chrome plating process, the two chrome layers S 1 and S 2 can be formed by
continuously moving the works W in the same chrome plating bath. Therefore, chrome plated parts having
excellent corrosion resistance and heat resistance can be produced efficiently.
In the above-mentioned embodiment, hard chrome plating is conducted in two steps so as to form the two
chrome layers S 1 and S 2 . However, in the present invention, the upper chrome layer S 2 may be omitted
and only the chrome layer S 1 may be formed on the work W. In this case, the crack-free chrome layer S 1 is
exposed to the outside and there is no oil sump for holding lubricating oil as in the case of the upper chrome
layer S 2 being formed on the lower chrome layer S 1 . However, the chrome layer S 1 is satisfactory in
terms of corrosion resistance.
Further, in the first embodiment, the lower chrome layer S 1 and the upper chrome layer S 2 are formed by
continuous operation using the apparatus shown in FIG. 3. However, in the present invention, a single
plating tank containing a chrome plating bath may be prepared and the lower chrome layer S 1 and the
upper chrome layer S 2 may be formed by batchwise operation using this plating tank. In this case, an
output of a current source is controlled by means of a controller so that a desired current density pattern of
an applied current, such as that shown in FIG. 2, can be obtained.
For batchwise operation, instead of using a single plating tank, a plating tank for forming the lower chrome
layer S 1 and a plating tank for forming the upper chrome layer S 2 may be separately provided, and the
lower chrome layer S 1 and the upper chrome layer S 2 may be formed by applying a pulse current to the
plating tank for forming the lower chrome layer S 1 and applying a direct current to the plating tank for
forming the upper chrome layer S 2 .
FIG. 4 shows a chrome plated part according to a second embodiment of the present invention. A feature of
this embodiment resides in that two intermediate chrome layers S 3 and S 4 are provided between the lower
chrome layer S 1 and the upper chrome layer S 2 . The properties of the intermediate chrome layers S 3 and
S 4 are not particularly limited. However, it is preferred that the intermediate chrome layer S 3 on a side of
the lower chrome layer S 1 has properties similar to those of the lower chrome layer S 1 and the
intermediate chrome layer S 4 on a side of the upper chrome layer S 2 has properties similar to those of the
upper chrome layer S 2 . Therefore, a few cracks F may be present in the intermediate chrome layer S 4 .
By providing the intermediate chrome layers S 3 and S 4 between the lower chrome layer S 1 and the upper
chrome layer S 2 , direct propagation of cracks from the upper chrome layer S 2 to the lower chrome layer S
1 can be suppressed, so that corrosion resistance of the chrome plated part can be stably maintained.
Although the two intermediate layers S 3 and S 4 are provided in this embodiment, the number of
intermediate chrome layers is not specifically limited in the present invention. A single intermediate layer
or three or more intermediate layers may be provided.
A chrome plated part in the second embodiment of the present invention can be obtained by, for example,
setting zones C 1 and C 2 between the above-mentioned zones A and B (FIG. 2) as shown in FIG. 5 and
setting a waveform of a pulse current in the zones C 1 and C 2 to the pattern different from that in the zone
A. With respect to an apparatus for obtaining the chrome plated part in the second embodiment,
substantially the same apparatus as the apparatus of FIG. 3 can be used, except that the front bus bar 9A
(FIG. 3) corresponding to the plating process tank 4B is divided into a plurality of bus bars which are
connected to different pulse current sources 12.
FIG. 6 is a chrome plated part according to a third embodiment of the present invention. A feature of this
embodiment resides in that an oxide film S 5 containing Cr 2 O 3 as a main component is formed as an
outermost layer of the chrome plated part. The oxide film S 5 is formed by conducting a heat oxidation
process after polishing (buffing) of the upper chrome layer S 2 . Due to the presence of the oxide film S 5 as
the outermost layer of the chrome plated part, corrosion resistance of the upper chrome layer S 2 itself can
be improved, to thereby prevent formation of white rust which is caused by corrosion of the chrome layer.
In the present invention, the oxide film may be formed solely from Cr 2 O 3 . Needless to say, when the
oxide film contains not only Cr 2 O 3 , but also a component other than Cr 2 O 3 in a small amount, the
oxide film is still satisfactory in terms of strength.
In order to conduct polishing and heat oxidation, an apparatus such as shown in FIG. 7 can be employed.
This apparatus comprises a primary line L 1 of production; a centerless polishing disk apparatus 20 provided
in the primary line L 1 ; a secondary line L 2 of production provided in parallel to the primary line L 1 ; a
pusher 21, a high-frequency coil 22 and a cooling coil 23 provided in the secondary line L 2 ; and an inclined
stand-by member 24 connected to the primary line L 1 and the secondary line L 2 . The centerless polishing
disk apparatus 20 comprises a buff wheel 20a and a regulating wheel 20b. After completion of the chrome
plating process, the work W is polished between the buff wheel 20a and the regulating wheel 20b of the
centerless polishing disk apparatus 20 and rolls on the inclined stand-by member 24 to the secondary line L 2
, where the work W is continuously moved through the high-frequency coil 22 and the cooling coil 23 by
extension of a rod 21a of the pusher 21. Thus, polishing and heat oxidation can be efficiently conducted.
EXAMPLE 1
Using rods (diameter: 12.5 mm; length: 200 mm) made of steel (JIS S25C) as test pieces. and a chrome
plating bath comprising 250 g/L of chromic acid, 2.5 g/L of sulfuric acid, 8 g/L of organic sulfonic acid and
10 g/L of boric acid, pulse plating was conducted under the following conditions: bath temperature=60° C.;
maximum current density I U =120 A/dm 2 ; minimum current density I L =0 A/dm 2 (the same as in the case
of FIG. 2); pulse time (on-time) T 1 at maximum current density I U =100 to 800 ?s; pulse time (off-time) T 2
at minimum current density I L =100 to 500 ?s; and frequency=0.8 to 5.0 kHz. As a result, a crack-free lower
chrome layer S 1 (FIG. 1) having a thickness of about 3 ?m was formed on a surface of each test piece.
Subsequently, in the same chrome plating bath, general-purpose plating was conducted at a bath
temperature of 60° C. and a current density of 60 A/dm 2 . As a result, an upper chrome layer S 2 (FIG. 1)
having a thickness of about 10 ?m was formed on the lower chrome layer S 1 on each test piece, to thereby
obtain samples 2 to 18 (as shown in Table 2). Further, for reference, using the same test piece and chrome
plating bath as mentioned above, general-purpose hard chrome plating was conducted at a bath
temperature of 60° C. and a current density of 60 A/dm 2 . As a result, a single chrome layer having a
thickness of about 20 ?m was formed on a surface of the test piece, to thereby obtain a sample 1.
With respect to the samples 2 to 18, a surface hardness (HV) was measured and visual observation was made
by using a microscope to evaluate formation of cracks in each of the lower and upper chrome layers S 1 and
S 2 after deposition. Further, with respect to the lower chrome layer S 1 , residual stress and crystal grain
size were measured as mentioned below. Further, the samples 2 to 18 were subjected to a salt-spray test in
accordance with JIS Z2371, and visually observed to evaluate occurrence of rusting. With respect to the
samples in which no rusting was observed, they were subjected to heat treatment at 200° C. for 2 hours.
The resultant samples were visually observed to evaluate formation of cracks on each of the lower and
upper chrome layers S 1 and S 2 in the above-mentioned manner, and were subjected to the salt-spray test
in accordance with JIS Z2371 again to evaluate occurrence of rusting. The color of a surface of each of the
samples 2 to 18 was observed at the time of completion of formation of the lower chrome layer S 1 . The
above-mentioned measurements and observations were also conducted with respect to the single chrome
layer of the sample 1.
Measurement of residual stress in the chrome layer was conducted by a method called "X-Sen Ouryoku
Sokuteihou (X-ray stress measurement method)" disclosed in "Hihakai Kensa (non-destructive inspection)",
vol. 37, item 8, pages 636 to 642, edited by The Japanese Society for Non-destructive Inspection.
Measurement of a crystal grain size of the chrome layer was conducted using an X-ray diffractometer, by
using a characteristic X-ray Cu-K? (wavelength: 1.5405620 ?) with respect to the Cr (222) diffraction plane.
In this measurement, the crystal grain size was determined by assigning the result of measurement of the
width (integral width) of a diffraction profile to the following Scherrer's equation. As the integral width, a
value corrected by a Cauchy function was used. D hkl =K??/? 1 cos ?
wherein
D hkl : crystal grain size (?) [measured in a direction perpendicular to (hkl)]
?: wavelength of an X-ray for measurement (?)
? 1 : width (integral width) of a diffraction beam dependent on the crystal grain size (rad)
?: Bragg angle of the diffraction beam
K: constant (1.05)
Results of the above-mentioned measurements and observations are shown in Table 2. TABLE 2 (1) Pulse
time Crystal Cracking of Residual Hard- Appear- Rusting (?s) grain size S 1 after stress ness ance of Before
heat After heat Evalu- Sample No. T 1 T 2 of S 1 (nm) deposition (MPa) (HV) of S 1 treatment treatment
ation 1 (Comparative) 6.1 Observed +230 1,090 Glossy Observed NG (2h) 2 (Comparative) 100 100 7.8
Observed +276 1,034 Glossy Observed NG (24h) 3 (Comparative) 200 100 8.0 Observed +160 1,017 Glossy
Observed NG (24h) 4 (Comparative) 150 150 8.2 Observed +10 940 Glossy Observed NG (96h) 5 (Comparative)
200 200 8.7 Not -65 920 Glossy Not Observed NG observed observed (24h) (300h) 6 (Present 150 200 9.6 Not
-150 870 Glossy Not Not OK invention) observed observed observed (300h) (300h) 7 (Present 100 200 9.8 Not
-203 835 Glossy Not Not OK invention) observed observed observed (300h) (300h) 8 (Present 110 220 10.1
Not -220 840 Glossy Not Not OK invention) observed observed observed (300h) (300h) 9 (Present 800 300
10.5 Not -205 818 Glossy Not Not OK invention) observed observed observed (300h) (300h) 10 (Present 400
300 10.6 Not -305 782 Glossy Not Not OK invention) observed observed observed (300h) (300h) 11 (Present
200 300 11.1 Not -339 742 Glossy Not Not OK invention) observed observed observed (300h) (300h) 12
(Present 300 300 11.7 Not -313 710 Glossy Not Not OK invention) observed observed observed (300H) (300h)
13 (Present 600 400 12.3 Not -323 681 Glossy Not Not OK invention) observed observed observed (300h)
(300h) 14 (Present 500 400 13.5 Not -334 630 Glossy Not Not OK invention) observed observed observed
(300h) (300h) 15 (Present 400 400 15.4 Not -272 602 Glossy Not Not OK invention) observed observed
observed (300h) (300h) 16 300 400 16.0 Observed +30 546 Milky Observed NG (Comparative) (96h) 17 600 500
16.7 Observed +53 498 Milky Observed NG (Comparative) (96h) 18 700 500 18.1 Observed +18 450 Milky
Observed NG (Comparative) (96h)
As shown in Table 2, with respect to the sample 1 (comparative) obtained by general-purpose hard chrome
plating, the chrome layer contained many cracks and rusting was observed over an entire surface of the
chrome layer at an extremely early time (2 hours) in the salt-spray test.
The samples 2 to 18 were obtained by the two-step plating process. Of these, with respect to the samples 2
to 4 and 16 to 18 (comparative), at the time of completion of the plating process, the upper chrome layer S
2 contained many cracks and the lower chrome layer S 1 was also cracked. When the samples 2 to 4 and 16
to 18 were subjected to the salt-spray test after the plating process, rusting was observed at a relatively
early time (24 to 96 hours) in the salt-spray test. Thus, with respect to the samples 2 to 4 and 16 to 18,
rusting occurred in the salt-spray test before heat treatment. Therefore, no heat treatment was conducted
with respect to these samples.
On the other hand, with respect to the samples 5 to 15 also obtained by the two-step plating process, at the
time of completion of the plating process, the upper chrome layer S 2 contained many cracks, but no
cracking was observed in the lower chrome layer S 1 . Further, with respect to the samples 5 to 15, no
rusting was observed until 300 hours after the start of the salt-spray test.
With respect to the samples 5 to 15 in which no rusting was observed before heat treatment, they were
subjected to heat treatment at 200° C. for 2 hours and visually observed to evaluate formation of cracks
and occurrence of rusting. With respect to the sample 5 (comparative), cracking was observed in the lower
chrome layer S 1 and rusting occurred at a relatively early time (24 hours) in the salt-spray test. On the
other hand, with respect to the samples 6 to 15 (present invention), no cracking was observed in the lower
chrome layer S 1 even after heat treatment and no rusting was observed until 300 hours after the start of
the salt-spray test.
Comparison was made between the samples 1 to 18 with respect to residual stress in the lower chrome layer
S 1 (the single chrome layer in the case of the sample 1). With respect to the samples 1 to 4 and 16 to 18
(comparative), the residual stress was tensile residual stress. With respect to the samples 5 to 15, the
residual stress was compressive residual stress. Especially, the samples 6 to 15 (present invention) had a
large compressive residual stress of 150 MPa or more.
Further, comparison was made between the samples 1 to 18 with respect to a crystal grain size of the lower
chrome layer S 1 (the single chrome layer in the case of the sample 1). With respect to the samples 1 to 5
(comparative), the crystal grain size was less than 9 nm. With respect to the samples 6 to 18, the crystal
grain size was 9 nm or more. In each of the samples 16 to 18, the chrome layer had an especially large
crystal grain size of 16 nm or more.
With respect to the surface hardness (HV), the surface hardness of the sample 1 (obtained by general-
purpose hard plating) was the highest. With respect to the remaining samples, the larger the crystal grain
size, the lower the surface hardness.
Further, comparison was made between the samples 1 to 18 with respect to the color of a surface of the
lower chrome layer S 1 (the single chrome layer in the case of the sample 1). With respect to the samples 1
to 15, the chrome layer had a glossy surface characteristic of chrome plating. With respect to the samples
16 to 18, the chrome layer had a milky surface.
From the above, it is apparent that formation of cracks in the chrome layer is dependent on the residual
stress and the crystal grain size of the chrome layer. In order to ensure a desired corrosion resistance of the
chrome plated part by suppressing cracking of the chrome layer even when it is subject to thermal
hysteresis, it is necessary to conduct the chrome plating process so that the lower chrome layer S 1 having a
compressive residual stress of 150 MPa or more, and preferably having a crystal grain size of 9 nm or more
can be obtained. The compressive residual stress which can be obtained solely by adjusting the waveform of
a pulse current is limited. Therefore, an appropriate waveform of a pulse current must be selected,
depending on the intended applications of the chrome plated part. With respect to the crystal grain size,
the lower chrome layer of each of the samples 16 to 18, which had a crystal grain size of 16 nm or more,
had tensile residual stress. Therefore, it is preferred that the crystal grain size be less than 16 nm.
EXAMPLE 2
Using the same test piece and chrome plating bath as used in Example 1, pulse plating was conducted under
the following conditions: bath temperature=60° C.; maximum current density I U =120 A/dm 2 ; minimum
current density I L =0 A/dm 2 ; pulse time (on-time) T 1 at maximum current density I U =1,400 ?s; pulse
time (off-time) T 2 at minimum current density I L =600 ?s; and frequency=500 Hz. As a result, a lower
chrome layer S 1 (FIG. 4) having a thickness of about 2 ?m was formed on a surface of the test piece.
Subsequently, in the same chrome plating bath, pulse plating was conducted under the following conditions:
bath temperature=60° C.; maximum current density I U =120 A/dm 2 ; minimum current density I L =0 A/dm
2 ; on-time T 1 =1,400 ?s; off-time T 2 =400 ?s; and frequency=625 Hz. As a result, an intermediate chrome
layer S 3 (FIG. 4) having a thickness of about 2 ?m was formed on a surface of the lower chrome layer S 1 .
Subsequently, in the same chrome plating bath, pulse plating was conducted under the following conditions:
bath temperature=60° C.; maximum current density I U =120 A/dm 2 ; minimum current density I L =0 A/dm
2 ; on-time T 1 =200 ?s; off-time T 2 =100 ?s; and frequency=3,333 Hz. As a result, an intermediate chrome
layer S 4 (FIG. 4) having a thickness of about 2 ?m was formed on a surface of the intermediate chrome layer
S 3 . Subsequently, in the same chrome plating bath, general-purpose plating was conducted at a bath
temperature of 60° C. and a current density of 60 A/dm 2 . As a result, an upper chrome layer S 2 (FIG. 4)
having a thickness of about 5 ?m was formed on the intermediate chrome layer S 4 , to thereby obtain a
sample.
With respect to the obtained sample, each of the lower chrome layer S 1 , the intermediate chrome layers S
3 and S 4 and the upper chrome layer S 2 was visually observed by using a microscope to evaluate formation
of cracks. Further, by the same methods as mentioned above in Example 1, residual stress and crystal grain
size were measured with respect to each of the chrome layers S 1 to S 4 . The sample was subjected to the
salt-spray test in accordance with JIS Z2371, and visually observed to evaluate occurrence of rusting. After
the salt-spray test, the sample was subjected to heat treatment at 200° C. for 2 hours, and subjected to the
salt-spray test in accordance with JIS Z2371 again. The resultant sample was visually observed to evaluate
occurrence of rusting. Results of the above-mentioned measurements and observations are shown in Table
3. TABLE 3 Crystal Rusting Residual grain Cracking Before After Chrome stress size after heat heat layer
(MPa) (nm) deposition treatment treatment S 1 -279 12.2 Not observed Not observed Not observed S 3 -163
10.7 Not observed S 4 +226 8.0 Slightly observed S 2 +300 6.6 Observed
As shown in Table 3, no cracking was observed with respect to the lower chrome layer S 1 and the
intermediate chrome layer S 3 . The intermediate chrome layer S 4 on a side of the upper chrome layer S 2
was slightly cracked and the upper chrome layer S 2 contained many cracks. With respect to the residual
stress, each of the lower chrome layer S 1 and the intermediate chrome layer S 3 had compressive residual
stress as large as more than 150 MPa. Each of the intermediate chrome layer S 4 and the upper chrome layer
S 2 had tensile residual stress. With respect to the crystal grain size, the crystal grain size of each of the
lower chrome layer S 1 and the intermediate chrome layer S 3 was as large as more than 9 nm. The crystal
grain size of each of the intermediate chrome layer S 4 and the upper chrome layer S 2 was much smaller
than 9 nm.
No rusting was observed in the salt-spray test before and after heat treatment. Therefore, it was
understood that the sample had sufficient corrosion resistance.
EXAMPLE 3
Using the same test pieces and chrome plating bath as used in Example 1, pulse plating was conducted
under the following conditions: bath temperature=60° C.; maximum current density I U =120 A/dm 2 ;
minimum current density I L =0 A/dm 2 ; pulse time (on-time) T 1 at maximum current density I U =300 ?s;
pulse time (off-time) T 2 at minimum current density I L =300 ?s; and frequency: 1.7 kHz. As a result, a
crack-free lower chrome layer S 1 (FIG. 1) having a thickness of about 3 ?m was formed on a surface of each
test piece. Subsequently, in the same chrome plating bath, general-purpose plating was conducted at a bath
temperature of 60° C. and a current density of 60 A/dm 2 . As a result, a cracked upper chrome layer S 2
(FIG. 1) having a thickness of about 10 ?m was formed on the lower chrome layer S 1 on each test piece. The
upper chrome layer S 2 was finished by buffing so as to have a surface roughness Ra of 0.08 ?m. As a result,
samples 31 and 32 were obtained. The sample 31 was subjected to a general-purpose baking process at 210°
C. for 4 hours, to thereby form an oxide film (containing Cr 2 O 3 as a main component) on the upper
chrome layer S 2 . The sample 32 was subjected to high-frequency heating at a maximum heating
temperature of 400° C. for a short period of time (about 10 seconds), to thereby form an oxide film
(containing Cr 2 O 3 as a main component) on the upper chrome layer S 2 .
For comparison, using the same test piece and chrome plating bath as used in Example 1, pulse plating was
conducted under the following conditions: bath temperature=60° C.; maximum current density I U =120
A/dm 2 ; minimum current density I L =0 A/dm 2 ; on-time T 1 =200 ?s; off-time T 2 =200 ?s; and
frequency=2.5 kHz. As a result, a crack-free lower chrome layer S 1 having a thickness of about 3 ?m was
formed on a surface of the test piece. Subsequently, in the same chrome plating bath, general-purpose
plating was conducted at a bath temperature of 60° C. and a current density of 60 A/dm 2 . As a result, a
cracked upper chrome layer S 2 having a thickness of about 10 ?m was formed on a surface of the lower
chrome layer S 1 , to thereby obtain a sample 33. The sample 33 was subjected to the above-mentioned
buffing and high-frequency heating. Further, for comparison, substantially the same procedure for obtaining
the sample 31 was repeated, except that the baking process was conducted before buffing, to thereby
obtain a sample 34.
With respect to each of the samples 31 to 34, residual stress and crystal grain size of the lower chrome layer
S 1 were measured by the same methods as mentioned above in Example 1. The samples 31 to 34 were
subjected to the salt-spray test in accordance with JIS Z2371, and visually observed to evaluate formation of
red rust and white rust. Results of the above-mentioned measurements and observations are shown in Table
4. TABLE 4 Crystal Residual grain stress Method Rusting Sample size of of S 1 of heat White Red No. Process S
1 (nm) (MPa) oxidation rust rust 31 Plating- 11.7 -313 Baking Not Not Polishing- observed observed Oxidation
32 Plating- 11.7 -313 High- Not Not Polishing- frequency observed observed Oxidation heating 33 Plating- 8.7
-65 High- Not Observed Polishing- frequency observed Oxidation heating 34 Plating- 8.7 -65 Baking Observed
Not Oxidation- observed Polishing
As shown in Table 4, in each of the samples 31 and 32, the lower chrome layer S 1 had sufficiently large
compressive residual stress and a sufficiently large crystal grain size. On the other hand, in each of the
samples 33 and 34, the lower chrome layer S 1 had undesirably low compressive residual stress and an
undesirably small crystal grain size.
After the salt-spray test, with respect to each of the samples 31 and 32 (present invention), red rust which
forms due to corrosion of a metallic substrate and white rust which forms due to corrosion of the chrome
layer were not observed. On the other hand, red rust was observed in the sample 33 (comparative) and
white rust was observed in the sample 34 (comparative). Red rust was observed in the sample 33 because
both of the lower chrome layer S 1 and the upper chrome layer S 2 contained cracks. White rust was
observed in the sample 34 because the oxide film formed by the baking process was removed by buffing.
FIG. 8 is a microphotograph showing white rust formed in the sample 34. No red rust was observed in the
sample 34 because, during buffing, the cracks were clogged due to the occurrence of plastic flow in the
chrome layer.
FIG. 9 is a graph showing a relationship between the thickness of plating and residual stress in the chrome
plated part of the present invention when pulse plating is conducted by application of the same pulse
current as used for obtaining the sample 12. In the graph, there is substantially no stress gradient such as
that shown in the above-mentioned Examined Japanese Patent Application Publication No. 43-20082.
Average compressive residual stress is stably maintained at a level of 100 MPa or more.
As has been described above, the chrome plated part of the present invention maintains excellent corrosion
resistance even when it is subject to thermal hysteresis. Therefore, the present invention is advantageous
when applied to products used in corrosive environments and under high temperature conditions. The
chrome plated part of the present invention is especially advantageous when it comprises a crack-free
chrome layer provided as the lowermost chrome layer and a cracked chrome layer provided as the
uppermost chrome layer, because such a chrome plated part has excellent wear resistance and excellent
sliding properties.
In the chrome plating method of the present invention, compressive residual stress and crystal grain size of
the chrome layer can be easily controlled by adjusting the waveform of a pulse current. Therefore, a
chrome plated part having desired properties can be efficiently obtained.
Further, in the method of the present invention for producing a chrome plated part, an oxide film
containing Cr 2 O 3 may be formed as an outermost layer of the chrome plated part. Therefore, formation
of red rust due to corrosion of a metallic substrate and formation of white rust due to corrosion of the
chrome layer can be surely prevented.
The present invention can be applied to a surface of a piston rod for a shock absorber or a surface of a piton
ring for an engine.
The entire disclosures of Japanese Patent Application Nos. 10-332047 and 11-285503 filed on Nov. 6, 1998
and Oct. 6, 1999, respectively, each including a specification, claims, drawings and summary are
incorporated herein by reference in their entirety.
Arvinda Kumar
R-9/303 Sector-9
Rajnagar Ghaziabad
NCR India 201002
+919818004652
1. A process for forming, on a substrate, a composite hard chromium coating comprising a disperse phase
and particularly suitable for mechanical components subjected to high-temperature chafing; the process
comprising the step of galvanically depositing at least one layer of hard chromium in a chromium plating
bath of the type forming microcracks and in which is dispersed in suspension a predetermined concentration
of given sized particles of a nonmetal insoluble in thebath;
characterized in that, in combination: (i)- in the course of said deposition step, the substrate is maintained
permanently at cathode potential; and a pulsating cathode current, varying cyclically in time between a
minimum and maximum value, is supplied to achieve a chromium layer comprising a matrix with microcracks
of a given distribution, and a disperse phase consisting of said nonmetal particles, some of which are
included in the microcracks, and some of which are directly embedded in the matrix; (ii)- said chromium
plating bath is a chromic acid based bath, containing in solution prevalently hexavalent chromium.
2. A process as claimed in Claim 1, characterized in that said deposition step is preceded by the step of
depositing on the substrate a continuous hard chromium base layer with substantially no microcracks or
porosity and which covers the whole of the substrate; said base layer being formed by galvanically
depositing chromium in a chromium plating bath of the type forming no microcracks.
3. A process as claimed in Claim 2, characterized in that, on said base layer, there are deposited
galvanically a number of said hard chromium layers, each comprising a microcracked matrix and a disperse
phase; said layers being so formed that the microcracks of each layer are offset depthwise in relation to the
microcracks of the adjacent layers.
4. A process as claimed in one of the foregoing Claims, characterized in that said nonmetal particles
insoluble in the bath consist of one or more materials in the group comprising: tungsten carbide, silicon
carbide, chromium carbide, aluminium oxide, silicon nitride, boron carbide, diamond, graphite, and
hexagonal boron nitride.
5. A process as claimed in one of the foregoing Claims, characterized in that, during the step of galvanically
depositing each said hard chromium layer comprising a microcracked matrix and a disperse phase consisting
of said particles embedded in the layer, the cathode current is supplied in a cycle comprising the following
steps: a first step wherein the cathode current is brought to and maintained for a first predetermined time
at a first threshold value other than zero; a second step, superimposed on the first, wherein the cathode
current is varied alternately, in a wave pattern and for a second predetermined time, between said first
threshold value and a second threshold value higher than the first; and a third step wherein the cathode
current is zeroed and maintained at zero for a third predetermined time.
6. A process as claimed in Claim 5, characterized in that, in said second step, the cathode current is varied
in a square wave pattern; and in said first and third steps, the cathode current is varied in steps.
7. A wear-resistant hard chromium coating, characterized in that it is formed using the process as claimed in
one of the foregoing Claims from 1 to 6, so as to present a relatively low hydrogen content A wear-resistant
hard chromium coating formed electrolytically, comprising a layer in turn comprising a microcracked hard
chromium matrix and a disperse phase, in the matrix, consisting of a number of particles of a nonmetal
material, and particularly suitable for mechanical components subjected to high-temperature chafing; a
first number of said particles being included in the microcracks of the matrix, and a second number of said
particles being embedded directly in parts of the matrix with no microcracks;
characterized in that, in combination: (i)- it comprises a first hard chromium layer with substantially no
microcracks or porosity and without said particles; and, deposited on said first layer, a number of said layers
comprising a microcracked matrix and a disperse phase consisting of said particles; (ii)- the microcracks of
said layers deposited on the first layer being provided offset depthwise in relation to the microcracks of the
adjacent layers.
8. A wear-resistant hard chromium coating as claimed in Claim 8, characterized in that the first layer
presents a thickness of at least 50 µm.
9. A wear-resistant hard chromium coating as claimed in Claim 8 or 9, characterized in that the width of the
microcracks, measured parallel to the layer, is at least 1 µm; the density of the microcracks ranges from 100
to 300 microcracks per centimeter; and the size of said nonmetal particles ranges from 0.1 to 20 µm.
Description:
The present invention relates to a process for forming, on a substrate, a composite hard chromium coating
comprising a disperse phase consisting of nonmetal particles; and to a wear-resistant coating formed using
such a process and particularly suitable for mechanical components subjected to high-temperature chafing,
such as internal combustion engine piston rings and components.
US Patent n. 4,846,940 relates to galvanic hard chromium coatings characterized by a Cr matrix with a large
number of micro- and macrocracks combined with a disperse phase, in the matrix, consisting of hard
particles embedded in the micro- and macrocracks of the matrix. Such coatings are formed by means of a
galvanic electrodeposition process characterized by comprising a current inversion step, i.e. by alternately
switching the substrate from cathode to anode potential and vice versa.
Such coatings present a small amount of incorporated hydrogen, a large number of even relatively large
cracks, and a large number of particle inclusions in the cracks, which make them highly susceptible to
corrosion. Moreover, depositing the coating by inverting the polarity of the electrodes poses practical
problems which complicate the fabrication process.
It is an object of the present invention to provide a process for forming hard chromium coatings comprising
at least one layer with a microcracked matrix and a disperse phase, and which is both straightforward and
economical while at the same time providing for good quality coatings characterized by a small amount of
incorporated hydrogen. It is a further object of the present invention to provide a composite hard chromium
coating of good quality and strength, which remains extremely hard even at high temperature, and which is
highly resistant to corrosion and wear both of itself and the mating part.
According to the present invention, there is provided a process for forming, on a substrate, a composite
hard chromium coating comprising a disperse phase and particularly suitable for mechanical components
subjected to high-temperature chafing; the process comprising the step of galvanically depositing at least
one layer of hard chromium in a chromium plating bath of the type forming microcracks and in which is
dispersed in suspension a predetermined concentration of given sized particles of a nonmetal insoluble in
the bath;
characterized in that, in the course of said deposition step, the substrate is maintained permanently at
cathode potential; and a pulsating cathode current, varying cyclically in time between a minimum and
maximum value, is supplied to achieve a chromium layer comprising a matrix with microcracks of a given
distribution, and a disperse phase consisting of said nonmetal particles, some of which are included in the
microcracks, and some of which are directly embedded in the matrix, said chromium plating bath is a
chromic acid based bath, containing in solution prevalently hexavalent chromium.
This provides for achieving a so-called "disperse chromium" coating comprising a Cr matrix containing
dispersing agents, which is extremely hard (over 1,000 Vickers), includes dispersing agents in the form of
nonmetal particles of hard materials such as oxides, carbides and nitrides of very low thermal conductivity
and high thermal stability, and which, combined with a low hydrogen content, presents a high degree of
thermal stability characterized by a reduced loss in hardness alongside an increase in temperature, and a
small amount of incorporated hydrogen in the Cr matrix. Moreover, variation of the cathode current may be
achieved easily using known facilities, and fully automatically by means of appropriate programming, thus
enabling troublefree, low-cost formation of the coating according to the present invention.
The above deposition step is preferably preceded by the step of depositing on the substrate a continuous
hard chromium base layer with substantially no microcracks or porosity, which covers the whole of the
substrate, and which is formed, preferably to a thickness of roughly 50 µm, by galvanically depositing
chromium in a chromium plating bath of the type forming no microcracks and containing no particles in
suspension. A number of said "disperse" layers comprising a microcracked Cr matrix and including hard
particles are then deposited successively on the continuous base layer.
The substrate-coating interface thus presents a fairly thick layer (in relation to the total thickness of the
coating, which is roughly 500 µm) with absolutely no cracks or dispersing agent particles (at least none
detectable by standard metallographic techniques), and which prevents the microcracks in the upper layers
of the coating from propagating towards the substrate, thus ensuring absolute protection of the substrate
and greatly enhancing the corrosion resistance of both the substrate and the coating.
When galvanically depositing each said hard chromium layer comprising a microcracked matrix and a
disperse phase consisting of said particles embedded in the layer, the cathode current is supplied according
to a cycle comprising the following steps:
* a first step wherein the cathode current is brought to and maintained for a first predetermined time at
a first threshold value other than zero;
* a second step, superimposed on the first, wherein the cathode current is varied alternately, in a wave
pattern and for a second predetermined time, between said first threshold value and a second threshold
value higher than the first; and
* a third step wherein the cathode current is zeroed and maintained at zero for a third predetermined
time.
More specifically, in said second step, the cathode current is varied in a square wave pattern; and in said
first and third steps, it is varied in steps.
The "disperse chromium" layers are therefore formed with the microcracks of one layer offset, depthwise of
the coating, in relation to those of the adjacent "disperse" layers, so that any depthwise propagation of the
microcracks in one layer (due to mechanical stress in the layer) is prevented from being transmitted to
those of the adjacent underlying layer, thus preventing the formation of macrocracks as in galvanic Cr
coatings formed using known processes. This provides for obtaining a much more stable coating, and for
further improving the corrosion resistance of the substrate, without, however, affecting the in-service
lubricant collecting and distribution function of the microcracks.
Finally, the presence of nonmetal dispersing agent particles substantially consisting of oxides (e.g.
aluminium oxide - Al 2 O 3 ) and/or carbides (tungsten, chromium, silicon, boron) and/or nitrides (silicon,
boron), i.e. extremely hard compounds, and both included inside the microcracks and embedded directly in
the chromium matrix, provides for obtaining a coating which is extremely resistant to wear caused by
abrasion or adhesion typical of high-temperature, mutually sliding metal surfaces.
The coating according to the present invention therefore comprises a layer comprising a microcracked hard
chromium matrix and a disperse phase, in the matrix, consisting of a number of particles of a nonmetal
material; a first number of said particles being included in the microcracks of the matrix, and a second
number of said particles being embedded directly in parts of the matrix with no microcracks; characterized
in that it comprises a first hard chromium layer with substantially no microcracks or porosity and without
said particles; and, deposited on the first layer, a number of said layers comprising a microcracked matrix
and a disperse phase consisting of said particles; the superimposed layers, deposited on the first layer,
presenting the microcracks offset depthwise in relation to those of the adjacent layers. Preferably, the first
layer presents a thickness of at least 50 µm; the width of the microcracks, measured parallel to the layer, is
at least 1 µm; the density of the microcracks ranges from 100 to 300 per centimeter; and the size of the
nonmetal particles embedded in the matrix ranges from 0.1 to 20 µm.
The favourable tribological properties of such coatings make them particularly suitable for sliding
components cooperating with cylinder liners, such as the piston rings of four- and two-stroke engines or
piston pumps, wherein the cylinder liners are normally made of lamellar, nodular or vermicular cast iron,
either natural or hardened (e.g. laser quenched) or nitrided (e.g. using the TENIFER (registered trade mark)
process or similar), or present surfaces with hot spray coatings such as FK1008 formed using the HVOF
process (both registered trade marks).
A number of non-limiting embodiments of the present invention will be described by way of example with
reference to the accompanying Figures, in which:
# Figure 1 shows a schematic section, perpendicular to the surface extension, i.e. in the direction of the
thickness, of a coating in accordance with the present invention;
# Figure 2 shows a hardness graph of different materials as a function of temperature;
# Figures 3, 4 and 5 show microphotographs of galvanic coatings formed using the process according to the
present invention;
# Figure 6 shows a graph of a spot EDS analysis of the Cr matrix of a coating in accordance with the present
invention.
Number 1 in Figure 1 indicates a wear-resistant coating formed according to the present invention on a
substrate 2, e.g. any known mechanical component made of cast iron. Coating 1 comprises a first layer 3,
preferably no more than 50 µm deep, formed of hard Cr, and characterized by being continuous, i.e. by
presenting no detectable microcracks or porosity, and no inclusions of any sort. On top of layer 3, there are
deposited a given number (four in the example) of substantially identical layers 5a, 5b, 5c, 5d, each
comprising a hard chromium matrix 6 in which are formed a number of microcracks 7 extending radially
depthwise of layer 5 towards substrate 2, and a disperse phase in matrix 6 and consisting of a number of
particles 8 of any hard nonmetal material.
According to the present invention, and as shown clearly, albeit schematically, in Figure 1, a first number of
particles 8 is included in microcracks 7 of matrix 6, and a second number of particles 8 is embedded directly
inside parts of matrix 6 with no microcracks 7; and the microcracks 7 of layers 5 deposited on first layer 3
are offset depthwise in relation to those of the adjacent layers 5. For example, as shown in the Figure 1
section, microcracks 7 of layer 5b extend depthwise towards underlying layer 5a and substantially towards
the portions between microcracks 7 of layer 5a, i.e. towards matrix 6 portions of layer 5a presenting no
microcracks. When viewed from above, the microcracks 7 of each layer 5 present a "spiderweb" pattern
along the interface surface 9 of each layer 5, as shown in Figure 5.
According to the present invention, the width of the microcracks, measured parallel to each layer 5, is at
least 1 µm; the microcrack density measured at surfaces 9 ranges from 100 to 300 microcracks per
centimeter of surface; and the size of nonmetal particles 8 ranges from 0.1 to 20 µm.
According to the present invention, a coating as described above may be formed electrolytically; layer 3
being formed by galvanically depositing Cr in known manner using any known chromium plating bath of the
type resulting in no microcracks and containing no particles in suspension, or operating accordingly with a
bath containing particles in suspension; and layers 5 being formed using known chromium plating baths of
the type for forming microcracks and containing particles 8 in suspension. A further precaution to ensure
layer 3 presents no microcracks is to limit its thickness, and to use such operating parameters (current
cycles and density, etc.) as to limit the formation of stress within the layer due to excessive energy supply.
According to the present invention, to achieve the above characteristics of layers 5 (particles 8 included
both inside the microcracks and directly in the matrix, and microcracks offset between one layer and
another), when depositing the layer on to the substrate (or underlying layer 5), substrate 2 is maintained
permanently at cathode potential, and a pulsating cathode current varying cyclically in time between a
minimum and maximum value is supplied. Also, the baths for forming layers 5 and containing particles 8 in
suspension are preferably agitated at all times, e.g. by means of mechanical, fluidodynamics, energetic
agitators, or by air injection.
The nonmetal particles 8 included in the coating must be insoluble in the baths which present a chromic
acid, sulphuric acid and catalyst base, are maintained at a temperature of about 55°C, and present a 20 to
400 gr/liter concentration of particles 8 (ranging in size between 0.1 and 20 micron). Particles 8 therefore
consist of one or more materials in the group comprising: tungsten carbide, silicon carbide, chromium
carbide, aluminium oxide, silicon nitride, boron carbide, diamond, graphite, hexagonal boron nitride. Each
layer 5 may of course include particles 8 all of the same material or of different materials, and likewise
from one layer to another.
The cathode current supply cycle comprises the following steps:
* a first step wherein the cathode current is increased in steps to a first threshold value other than zero
(roughly 70 amps per square decimeter) and maintained at that value for a first predetermined time ranging
from 10 to 60 seconds;
* a second step, superimposed on the first, wherein the cathode current is varied alternately, in a square
wave pattern, between the first threshold value and a second threshold value higher than the first; in
particular, using a pulse amplitude of 0.2-0.5 times the first threshold value, i.e. 0.2-0.5 x 70 = 14-35 A/dm
2 , and an oscillation period of 0.01 to 1 second; and for a time ranging from 10 to 60 seconds;
* a third step wherein the cathode current is zeroed in steps and maintained at zero for a third
predetermined time ranging from 0.03 to 60 seconds.
The following is a non-limiting embodiment by way of example of the present invention.

EXAMPLE
Using a 1500 lt tank, a bath with the following composition is prepared:

CrO 3 250.0 gr/lt; FeSiF 6 1.5 gr/lt;
H 2 SO 4 2.5 gr/lt SiC (*) 50.0 gr/lt; (*) particle size: 50% of 2.5 µm
Lead anodes and a cathode consisting of rings of lamellar cast iron are immersed in the bath, and a
chromium coating is deposited, agitating the bath by recirculating roughly 300 lt/min and injecting air at
roughly 5 bar pressure, and operating with a potential difference of 15 volts and a continuous cathode
current of a mean density of 70 A per square decimeter, which is varied during deposition according to the
following cycle:
* a first step wherein the cathode current is increased in steps from zero to 70 A/dm 2 and maintained at
that value for 20 seconds;
* a second step, superimposed on the first, wherein the cathode current is oscillated in a square wave
pattern with a bandwidth of 18 A/dm 2 and a frequency of 16 Hz for the same time of 20 seconds;
* a third step wherein the cathode current is zeroed in steps and maintained at zero for 0.03 seconds;
* repetition of the cycle from the beginning.
This eventually produces the coating shown in the Figure 4 section, which presents excellent adherence at
the coating-substrate interface. The Figure 3 photograph (enlarged 625 times) of the unetched coating, and
the similar top plan view in Figure 5 show the characteristics of the coating: good adherence, low
microcrack density, and inclusion of silicon carbide particles both inside and outside the cracks. This is
confirmed by EDS analysis (Figure 6) of specimen pieces, which shows the typical Cr and Si peaks of a spot
analysis of the matrix far from the cracks.
- Hard Chromium Plating

The ring is plated on its outer diameter surface with chromium to a depth of around 0.1 mm. The surface is
then lapped in a pot to get a slight barrel profile and to achieve light-tightness. Chromium plating provides a
very hard and wear-resistant surface.
- Molybdenum
The ring is machined with a shallow groove on its outer surface and this groove is filled with molybdenum
either by means of wire spray or plasma spray (the latter uses molybdenum in powdered form). Molybdenum
is a very hard material and it is extremely wear and scuff resistant. It is more scuff resistant than chromium
partly due to the slightly porous nature of the surface which absorbs oil. There are instances where
chromium will scuff and molybdenum will resist scuffing in the same engine. It is possible to molybdenum
coat the entire outer surface rather than just in a groove - this will depend upon the technique employed by
the ring manufacturer.
- Steel Compression Rings

Over the last 10 or so years, in many new engines steel has been used as a top ring material instead of cast
iron. The reason for this is that it is easier to achieve the very narrow widths that are becoming common,
and also the radial depth can be reduced to make the ring more conformable to out-of-round bores. The
rings are very strong and
wear resistant. However, like SG iron, they need to be treated on their outer diameters to prevent scuffing
and wear. Again, like cast iron top rings, steel top rings can be chromium plated or molybdenum inlaid (the
steel is pre- grooved when it is drawn), or it can be full face coated with molybdenum using a plasma spray
process. In addition it is possible to nitrocarburise steel rings. This process hardens the whole of the ring, ie
its OD surface as well as its sides, so the resistance to side wear is also enhanced. Nitrocarburising is carried
out in a liquid bath or in a gaseous atmosphere. As with the cast iron rings, the nitrocarhurised steel rings
are lapped in a pot to achieve a slight barrel profile and light-tightness. There is a difference between the
types of steel used for chromium or molybdenum coated rings, and that used if the surface is to be
nitrocarburised. If the outer surface is be coated with chromium or molybdenum, there is no need to have a
heat-treatable steel - so a steel with low alloy content is normally used. If the ring is to be nitrocarhurised,
the steel needs to be higher in chromium, nickel and other alloying elements to facilitate heat treatment.
Steel top rings are now used in the vast majority of new engines. However for most engines being built up
for performance applications in the aftermarket, cast iron rings are generally chosen since they are in fact
more ductile than steel, and it is possible to file back the gaps for file-back applications.
- Compression Ring Design

For a compression ring to perform adequately, it is essential that it exerts some pressure against the
cylinder to maintain a light seal. When combustion occurs, the combustion gases cannot pass this light seal
between the cylinder and the ring. The high pressure gas
enters the ring groove and pushes the ring down strongly against the bottom of the ring groove and out
against the cylinder creating a very effective seal. This initial light sealing action, sometimes in combination
with a downward scraping profile of the ring, also helps scrape a small amount of oil off the cylinder wall,
ensuring good oil control.
Compression rings are manufactured with a free gap so that when they are compressed into the cylinder
they push outwards to create this critical initial light seal. In the installed condition, compression rings must
be circular to match the cylinder. They can be designed to have a uniform contact pressure against the
cylinder around the entire circumference of the ring, or have higher or lower pressure at the gaps. Low tip
pressure rings are often used in two stroke engines where the rings are free to rotate. This reduces the
possibility of the gaps of the ring protruding into the cylinder ports and being broken off as the piston moves
up and down. High tip pressure rings are designed to create extra damping (or friction) at the ring gap to
raise the speed at which ring lifting or flutter occurs (ring flutter is associated excessive amounts of
blowby). However, increased wear occurs at the areas of higher pressure while the areas of lower pressure
(at the two and ten o'clock position) can allow leakage to occur, especially in distorted cylinders or if the
radial depth of the ring is high, making it too stiff to conform. Complex mathematics are required to
calculate the special non-round cam shapes that a compression ring requires in the free state, in order that
it obtain these various ideal pressure patterns. This special cam shape is machined into compression rings
early in the manufacturing process. Factors such as material variations, casting and machining residual
stresses and radial depth variations need to be controlled in the manufacture of compression rings to
minimise variations from the mathematical ideal.
- Second Rings
Second rings are primarily there to assist the oil ring to prevent upward movement of oil. The reverse
torsional twist ring is especially effective because it twists downwards in its groove. As a result, its lower
edge seals against the bottom outer corner of the second ring groove and this prevents oil from bypassing
the ring on the downward stroke of the piston. On the upward stroke, the high taper angle allows oil to pass
by the ring rather than be scraped upwards. Second rings must be fitted in the groove the correct way. Most
second rings have a "dot" to signify the upper side though in some instances the manufacturer's name is
stamped on the upper side. Regular grey iron is almost always used in second grooves. Where it differs from
SG is that it has the ability to run against a bore uncoated and it is very scuff resistant. It is not as hard as
SG. It beds in very quickly. Naturally it is not as strong as SG iron but in a second groove the strength
requirement is not the same as in a top groove. What if no second rings are used? It is possible to delete the
second rings in a performance application. Doing this, in conjunction with a file back top ring (with a fairly
small gap) can reduce friction, and it can also allow the piston
to be shorter in the ring belt region with consequent weight savings. However if oil consumption is to be
kept under control the oil ring needs to have more load, and this negates friction benefits. However blowby
can be less with only one compression ring. Formula One engines have only one compression ring.
- Ring Gaps
One minor avenue remains for gas escape is the area bounded by the gap end clearance, which is necessary
to prevent ring ends butting at operating temperature. End clearance on piston rings is controlled within
0.07 to 0.12mm per 25mm of bore size, being of lower value than this under engine operating conditions -
hence there is only a very small area for gas to pass. Piston ring manufacturers supply rings, whether for
original equipment or aftermarket, pre-gapped. The diameter to which pre-gapping is carried out will be
nominal bore diameter, whereas in practice bore sizes may vary according
to the grade - some engine manufacturers have as many as 15 grades, covering 0.1mm increments though
the tendency is for less. It is, therefore, conceivable for piston rings
as supplied to have more gap than the ring manufacturers' specification. In most cases this increase in gap
does not matter. It must be remembered that there are two compression rings and in any case the
combustion process takes place in milliseconds and there is simply not time for significant leakage to occur.
During operation of an engine, blowby passing through the ring gap is under very high pressure and it
reaches what is termed "sonic velocity". At this point any increase will not result in any increase in
gas velocity (hence the rate of escape of the gases). From this point of view, leak-down tests are of little or
no value in determining engine condition, as they measure leakage under static and low pressure conditions.
Gap Types Most gaps are straight cut, however,
there are applications requiring different gap types. Oil ring gaps are of even less significance. While
production rings may have gaps specified at 1.00mm nominal, up to 1.75mm would be satisfactory in most
cases, again keeping in mind the labyrinth effect with gaps spaced apart. The gas which does escape the
piston rings, and which is returned to the intake charge, is termed blowby. The control of blowby to an
acceptable level is important because excessive blowby means loss of engine power, leads to ring sticking
and an increase in emissions. That is why manufacturers tightly control piston ring shape and flatness, two
factors important for good gas sealing. Blowby is measured under laboratory conditions by sealing off the
engine's crankcase and attaching an accurate gas meter by means to the breather on the oil filler cap. A
typical 2-litre engine can expected to have a blowby figure of 20-30 litres per minute under full load
conditions. So that the upward passage of oil around and behind the compression rings is controlled,
compression rings must have proper seating on the lower
faces of the piston ring grooves, just as proper seating is necessary for the control of blowby. The control of
oil past the ring faces relies on the ring face attitude to the cylinder wall and the quick seating or bedding-
in of the ring face. Bedding-in or mating of the rings with the cylinders is the initial wear of both rubbing
surfaces necessary to render them compatible during operation and consistent with the establishment of an
oil and gas seal. The attitude of the ring face to the cylinder wall must at all times be "downward scraping"
to carry the excess oil on the cylinder walls downwards ahead of it. For this reason, the top edge of the
compression ring must never be the only portion of the ring face to be touching the bore - if it were, it
would have an upward scraping effect and would cause a very high rate of oil consumption.
- Oil Control Rings

In engine lubricating systems much more oil is thrown onto the cylinder walls than is necessary for piston
and ring lubrication. To prevent excessive oil consumption (and a smoky exhaust!) each piston is supplied
with one or two oil control rings which are placed in piston grooves below those for compression rings. The
prime function of the oil control ring is to scrape excess quantities of oil from the cylinder walls and to
return it to the crankcase through draining areas, and, secondly, to meter sufficient oil to satisfactorily
lubricate the compression rings. Requirements by engine manufacturers for lower oil consumption led to the
introduction of segmental oil rings. There are two basic types of segmental oil rings; both types have two
steel rails for scraping oil from the cylinder walls,
however, one type uses a wave form shaped expander and a cast iron or pressed steel spacer, while the
other has a circumferential abutment spacer- expander to provide outward force on the steel rails. By far
the most common is the three piece circumferential type. Conformability to "out-of-round" cylinder bores of
both types of segmental oil rings is excellent and they also have the ability of sealing the rails against the
groove side faces. This is effected by the design of the circumferential expander which has a large number
of angled tabs protruding for rail support. When the assembly is compressed into a bore, a portion of the
load applied by the expander is imparted to the steel rails in the direction of the side faces. Segmental oil
rings have a degree of independent rail action, which means both rails contact the bore even when the bore
shows some degree of wear or taper, or with short skirt pistons with higher piston-to-bore attitude angles.
Oil control is therefore maintained. The steel rails are chromium plated for compatibility with cylinder walls
(since the carbon steel would quickly scuff if not coated) and for wear resistance. The scraping edge is
designed to have a high contact pressure for quick "bed-in" on both newly honed and worn cylinder surfaces.
Less popular and less effective – but still in use - is the unitised oil ring. This has two rails, a sine wave
expander and a spacer. Its load is derived from compression of the sine wave expander against the back of
the oil ring groove and therefore relies upon the accuracy
of machining of the piston groove for correct wall pressure. Wall Pressure (or oil ring load)
While the compression rings derive most of their wall pressure from the combustion gas pressure, oil rings
must generate their own wall pressure. The expander can be thought of simply as a compression spring. It is
longer in length when in the free state than when compressed into the bore and it is the difference in these
two lengths that determines the load (and hence wall pressure) for a given expander. A typical amount of
compression is 4mm for an 80mm bore, but this can vary according to the spring rate of the expander. A
stiff expander has a high spring rate and deflects less on entry to the bore, but will lose load more rapidly as
wear takes place. A low spring rate expander will show less load drop off with wear, but has greater
deflection. If the deflection is too great, assembly of the rails may be difficult since the rails may protrude
over the edge of the ring load during assembly. This is known as popout, or necklacing. Typical wall
pressures for new engines in the 80-100mm bore size may be 1 MPa, but some aftermarket manufacturers
make assemblies with wall pressures as high as 2MPa. This may control oil better initially, but leads to rapid
wear and greater friction losses.
- Expander Types (Circumferential)

There are numerous types of circumferential expanders in common usage. In general terms equivalent
performance may be obtained from carbon steel and stainless steel types and within both there are
numerous shapes and types. Once installed, the important factors are wall pressure and conformability, the
latter a function of the rail radial depth. There is a trend towards the lowering of loads and a reduction in
radial depth in the interest of reduced engine friction. Reduced radial depth allows greater conformability
to an out-of-round or distorted bore and as a consequence, the compressive load exerted by the expander
does not have to be as high in order to give sealing around the rings outer periphery.
This anode composition comprises about 1 to 20% and preferably about 1.5% by weight of silver, about 3 to 8%
and preferably about 5% by weight of antimony, about 2 to 6% and preferably about 3% by weight of tin, and with
the principal constituent of the balance being lead. The silver content provides corrosion resistance preventing
rapid deterioration in use of the anode and the antimony content increases the strength and rigidity of the anode.
The tin content promotes formation of an oxide film on the surface of the anode which enhances the rate of
oxidation of the trivalent chromium to hexavalent chromium.

Electroplating Theory & Concepts - Beginners Edition

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Chromium Plating

Vice President of Technology

Kearny, New Jersey

CHROMIC-ACID-BASED BATHS (Hexavalent type)

Table I—Single Catalyst Plating Bath Parameters:

Decorative Hard (heavy) plating

Co-Catalyzed and High-Speed Baths

1. Effect of chromic acid concentration on current efficiency.

Self-Regulating High-Speed Baths

3. Membrane separating anode box from cathode compartment in trivalent

TRIVALENT CHROMIUM PLATING

Single-Cell Trivalent Chromium

—Dr. Donald L. Snyder

World Wide Technical

Comparison of Effluent Treatment for Cr+6 and Cr+3

Table III—Metallic Impurities and Their Effects on Trivalent Baths

Cr2(SO4)3 + Na2SO4 + 3H2O

Hexavalent Chromium Plating Troubleshooting Guide

Table A—Working Parameters of Single-Cell Trivalent Baths

Possible Cause: Corrective Step:

Too high temperature

Possible Cause: Corrective Step:

Table IV—Conversion of Excess Sulfate to Barium Carbonate Required

Note: 1 oz/gal = 7.5 g/liter

5. Cathode selector for use in reoxidation of trivalent chromium

Vice President of Technology

Kearny, New Jersey

CHROMIC-ACID-BASED BATHS (Hexavalent type)

Co-Catalyzed and High-Speed

1. Effect of chromic acid concentration on current efficiency.

Self-Regulating High-Speed Baths

Cleaning and Surface Preparation

TRIVALENT CHROMIUM PLATING

Single-Cell Trivalent Chromium

—Dr. Donald L. Snyder

World Wide Technical

Comparison of Effluent Treatment for Cr+6 and Cr+3

Table III—Metallic Impurities and Their Effects on Trivalent Baths

CrO3 + 2 NaHSO3 + 2H2SO4

Cr2(SO4)3 + Na2SO4 + 3H2O

Hexavalent Chromium Plating Troubleshooting Guide

Table A—Working Parameters of Single-Cell Trivalent Baths

Deposit structure Microporous Microporous

Possible Cause: Corrective Step:

Possible Cause: Corrective Step:

Possible Cause: Corrective Step:

Possible Cause: Corrective Step:

Too high temperature

Table IV—Conversion of Excess Sulfate to Barium Carbonate Required

Excess sulfate Barium Carbonate Required (oz)

Note: 1 oz/gal = 7.5 g/liter

Table V—Conversion of Excess Sulfate to Barium Carbonate Required

5. Cathode selector for use in reoxidation of trivalent chromium.

An overview of decorative and hard chromium electroplating processes

Decorative Hex Electrolytes

Calculation of Plating Times

Decorative Trivalent Electrolytes

Hard Chrome Plating

* High hardness

Decorative and Hard Chromium Electroplating

By Allen R. Jones and Donald Snyder

Atotech USA Inc.